Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and alpha-olefin/conjugated diene copolymers

ABSTRACT

The invention provides a process using olefin polymerization catalysts exhibiting excellent polymerization activities. The olefin polymerization catalysts of the invention contain a transition metal compound of and at least one of an organometallic compound, an organoaluminum oxy-compound or a compound which reacts with said transition metal compound to form an ion pair. The process using the inventive catalysts is useful in producing α-olefin/conjugated diene copolymers having specific properties.

CROSS-REFERENCE OF APPLICATIONS

This application is a divisional of co-pending application Ser. No.09/942,706, filed on Aug. 31, 2001, which is a divisional of U.S. Pat.No. 6,309,997 issued Oct. 30, 2001, the entire contents of which arehereby incorporated by reference, and for which priority is claimedunder 35 U.S.C. § 120; and this application claims priority ofApplication No. 109922/1997; 111439/1997; 132333/1997; and 50541/1998filed in Japan on Apr. 25, 1997; Apr. 28, 1997; May 22, 1997; and Mar.3, 1998, respectively, under 35 U.S.C. § 119.

FIELD OF THE INVENTION

The present invention relates to novel olefin polymerization catalysts,transition metal compounds and processes for olefin polymerization usingthe olefin polymerization catalysts.

The present invention also relates to α-olefin/conjugated dienecopolymers which have narrow molecular weight distribution and arefavorably used as rubbers.

BACKGROUND OF THE INVENTION

As olefin polymerization catalysts, “Kaminsky catalysts” are well known.The Kaminsky catalysts have extremely high polymerization activities,and by the use of them, polymers of narrow molecular weight distributioncan be obtained. Transition metal compounds which are known as thoseemployable for the Kaminsky catalysts are, for example,bis(cyclopentadienyl)zirconium dichloride (see: Japanese PatentLaid-Open Publication No. 19309/1083) and ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride (see: Japanese PatentLaid-Open Publication No. 130314/1086). It is also known that the olefinpolymerization activities or the properties of the resulting polyolefinsgreatly vary when different transition metal compounds are used in thepolymerization. Further, transition metal compounds having a ligand ofdiimine structure have been recently proposed as novel olefinpolymerization catalysts (see: International Patent Publication No.9623010).

By the way, polyolefins generally have excellent mechanical properties,and therefore they are used in many fields such as fields of variousmolded products. However, with variation of requirements for thepolyolefins, polyolefins of various properties have been desired inrecent years. Moreover, increase of productivity has been also desired.

Under such circumstances as mentioned above, there has been desireddevelopment of olefin polymerization catalysts having excellent olefinpolymerization activities and capable of producing polyolefins ofexcellent properties.

It is well known that copolymerization of several kinds of α-olefins andnon-conjugated dienes proceeds when Ziegler-Natta polymerizationcatalysts are used. Since the copolymers thus obtained are useful asrubbers, copolymers of various types have been produced. However, thenon-conjugated dienes used in the copolymerization are generallyexpensive and have low reactivity. Therefore, diene components which areinexpensive and have high reactivity are desired.

Examples of such diene components include conjugated dienes such as1,3-butadiene and isoprene. Though these conjugated dienes are moreinexpensive and have higher reactivity as compared with the conventionalnon-conjugated dienes, they have problem such that the activities aremarkedly lowered or only ununiform copolymers of wide compositiondistribution or wide molecular weight distribution are obtained if thecopolymerization is conducted by the use of the conventionalZiegler-Natta polymerization catalysts. In case of a Ziegler-Nattacatalyst system using a vanadium compound, the polymerization activitiesare extremely low, though relatively uniform copolymers are obtainable.In the circumstances, copolymerization of ethylene and butadiene usingmetallocene catalysts which have been studied extensively and thus knownto exhibit high polymerization activities has been investigated(National Publication of International Patent No. 501633/1989).

In the above case, however, it has been reported that from the dieneunit and ethylene incorporated into the polymer form togethercyclopentane skeleton in the polymer chain, and that the proportion ofthe cyclopentane skeleton becomes not less than 50% of all the dieneunits. The conversion of double bonds of the diene unit into thecyclopentane skeleton is very disadvantageous in the procedure of“vulcanization” required to use the copolymers as rubbers. Further, thecyclopentane skeleton is an unfavorable skeleton because it functions toincrease glass transition temperature of the copolymers and isdetrimental to the low-temperature properties of the rubbers.

Under these circumstances, as mentioned above, there has been eagerlydesired development of copolymers of α-olefins and conjugated dienes,which have narrow molecular weight distribution and uniform compositionand contain almost no cyclopentane skeleton in their polymer chains.

OBJECT OF THE INVENTION

It is an object of the present invention to provide an olefinpolymerization catalyst having excellent olefin polymerizationactivities.

It is another object of the invention to provide a novel transitionmetal compound useful for such catalyst.

It is a further object of the invention to provide a process for olefinpolymerization using the catalyst.

It is a still further object of the invention to provide anα-olefin/conjugated diene copolymer having a narrow molecular weightdistribution and containing almost no cyclopentane skeleton in itspolymer chain.

SUMMARY OF THE INVENTION

The first olefin polymerization catalyst according to the presentinvention comprises:

-   -   (A) a transition metal compound represented by the following        formula (I), and    -   (B) at least one compound selected from:        -   (B-1) an organometallic compound,        -   (B-2) an organoaluminum oxy-compound, and        -   (B-3) a compound which reacts with the transition metal            compound (A) to form an ion pair:            wherein M is a transition metal atom of Group 3 to Group 11            of the periodic table,    -   m is an integer of 1 to 6,    -   R¹ to R⁶ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, an oxygen-containing group, a        nitrogen-containing group, a boron-containing group, a        sulfur-containing group, a phosphorus-containing group, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and two or more of them may be bonded to        each other to form a ring,    -   when m is 2 or greater, two of the groups R¹ to R⁶ may be bonded        to each other, with the proviso that the groups R¹ are not        bonded to each other,    -   n is a number satisfying a valence of M, and    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group, an        oxygen-containing group, a sulfur-containing group, a        nitrogen-containing group, a boron-containing group, an        aluminum-containing group, a phosphorus-containing group, a        halogen-containing group, a heterocyclic compound residue, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and when n is 2 or greater, plural groups        X may be the same or different and may be bonded to each other        to form a ring.

In the present invention, R⁶ in the formula (I) is preferably a halogenatom, a hydrocarbon group, a heterocyclic compound residue, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group.

In the present invention, the transition metal compound represented bythe formula (I) is preferably a transition metal compound represented bythe following formula (I-a):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table,

-   -   m is an integer of 1 to 3,    -   R¹ to R⁶ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, a hydrocarbon-substituted silyl group, a        hydrocarbon-substituted siloxy group, an alkoxy group, an        alkylthio group, an aryloxy group, an arylthio group, an acyl        group, an ester group, a thioester group, an amido group, an        imido group, an amino group, an imino group, a sulfonester        group, a sulfonamido group, a cyano group, a nitro group, a        carboxyl group, a sulfo group, a mercapto group or a hydroxyl        group, and two or more of them may be bonded to each other to        form a ring,    -   when m is 2 or greater, two of the groups R¹ to R⁶ may be bonded        to each other, with the proviso that the groups R¹ are not        bonded to each other,    -   n is a number satisfying a valence of M, and    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group, an        oxygen-containing group, a sulfur-containing group, a        nitrogen-containing group, a boron-containing group, an        aluminum-containing group, a phosphorus-containing group, a        halogen-containing group, a heterocyclic compound residue, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and when n is 2 or greater, plural groups        X may be the same or different and may be bonded to each other        to form a ring.

In the above formula (I-a), R⁶ is preferably a halogen atom, ahydrocarbon group, a heterocyclic compound residue, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, a arylthiogroup, an acyl group, an ester group, a thioester group, an amido group,an imido group, an amino group, an imino group, a sulfonester group, asulfonamido group, a cyano group, a nitro group, a carboxyl group, asulfo group, a mercapto group or a hydroxyl group.

Further, the transition metal compound represented by the formula (I) ispreferably a transition metal compound represented by the followingformula (I-a-1):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table,

-   -   m is an integer of 1 to 3,    -   R¹ to R⁶ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, a hydrocarbon-substituted silyl group, a        hydrocarbon-substituted siloxy group, an alkoxy group, an        alkylthio group, an aryloxy group, an arylthio group, an acyl        group, an ester group, a thioester group, an amido group, an        imido group, an amino group, an imino group, a sulfonester        group, a sulfonamido group, a cyano group, a nitro group or a        hydroxyl group, and two or more of them may be bonded to each        other to form a ring,    -   when m is 2 or greater, two of the groups R¹ to R⁶ may be bonded        to each other, with the proviso that the groups R¹ are not        bonded to each other,    -   n is a member satisfying a valence of M, and    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1        to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20        carbon atoms, an oxygen-containing group, a sulfur-containing        group or a silicon-containing group, and when n is 2 or greater,        plural groups X may be the same or different and may be bonded        to each other to form a ring.

In the formula (I-a-1), R⁶ is preferably a halogen atom, a hydrocarbongroup, a heterocyclic compound residue, a hydrocarbon-substituted silylgroup, a hydrocarbon-substituted siloxy group, an alkoxy group, analkylthio group, an aryloxy group, an arylthio group, an acyl group, anester group, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group.

In the present invention, further, the transition metal compoundrepresented by the formula (I) is preferably a transition metal compoundrepresented by the following formula (I-b):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table,

-   -   m is an integer of 1 to 6,    -   R¹ to R⁶ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a        hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy        group, an ester group, an amido group, an amino group, a        sulfonamido group, a cyano group or a nitro group, and two or        more of them may be bonded to each other to form a ring, and    -   when m is 2 or greater, two of the groups R¹ to R⁶ may be bonded        to each other, with the proviso that the groups R¹ are not        bonded to each other.

In the formula (I-b), R⁶ is preferably a halogen atom, a hydrocarbongroup, a hydrocarbon-substituted silyl group, an alkoxy group, anaryloxy group, an ester group, an amido group, an amino group, asulfonamido group, a cyano group or a nitro group.

It is preferred that M in the transition metal compound (A) is at leastone transition metal atom selected from Groups 3 to 5 and Group 9 of theperiodic table.

The first olefin polymerization catalyst according to the invention mayfurther comprise a carrier (C), in addition to the transition metalcompound (A) and at least one compound (B) selected from theorganometallic compound (B-1), the organoaluminum oxy-compound (B-2) andthe compound (B-3) which reacts with the transition metal compound (A)to form an ion pair.

The first process for olefin polymerization according to the presentinvention comprises polymerizing or copolymerizing an olefin in thepresence of the above-mentioned olefin polymerization catalyst.

The second olefin polymerization catalyst according to the presentinvention comprises:

-   -   (A′) a transition metal compound represented by the following        formula (II), and    -   (B) at least one compound selected from:        -   (B-1) an organometallic compound,        -   (B-2) an organoaluminum oxy-compound, and        -   (B-3) a compound which reacts with the transition metal            compound (A′) to form an ion pair.            wherein M is a transition metal atom of Group 3 to Group 11            of the periodic table,    -   R¹ to R¹⁰ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, an oxygen-containing group, a        nitrogen-containing group, a boron-containing group, a        sulfur-containing group, a phosphorus-containing group, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and two or more of them may be bonded to        each other to form a ring,    -   n is a number satisfying a valence of M,    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group, an        oxygen-containing group, a sulfur-containing group, a        nitrogen-containing group, a boron-containing group, an        aluminum-containing group, a phosphorus-containing group, a        halogen-containing group, a heterocyclic compound residue, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and when n is 2 or greater, plural groups        X may be the same or different and may be bonded to each other        to form a ring, and    -   Y is a divalent bonding group containing at least one element        selected from the group consisting of oxygen, sulfur, carbon,        nitrogen, phosphorus, silicon, selenium, tin and boron, and when        it is a hydrocarbon group, the hydrocarbon group has 3 or more        carbon atoms.

In the above formula (II), at least one of R⁶ and R¹⁰ is preferably ahalogen atom, a hydrocarbon group, a heterocyclic compound residue, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group. The transition metal compound represented by theformula (II) is preferably a transition metal compound represented bythe following formula (II-a).

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table,

-   -   R¹ to R¹⁰ may be the same or different, they are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a        hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy        group, an ester group, an amido group, an amino group, a        sulfonamido group, a cyano group or a nitro group, and two or        more of them may be bonded to each other to form a ring,    -   n is a number satisfying a valence of M,    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1        to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20        carbon atoms, an oxygen-containing group, a sulfur-containing        group or a silicon-containing group, and when n is 2 or greater,        plural groups X may be the same or different and may be bonded        to each other to form a ring, and    -   Y is a divalent bonding group containing at least one element        selected from the group consisting of oxygen, sulfur, carbon,        nitrogen, phosphorus, silicon, selenium, tin and boron, and when        it is a hydrocarbon group, the hydrocarbon group has 3 or more        carbon atoms.

In the above formula (II-a), at least one of R⁶ and R¹⁰ is preferably ahalogen atom, a hydrocarbon group, a hydrocarbon-substituted silylgroup, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup.

It is preferred that M in the transition metal compound (A′) is at leastone transition metal atom from Groups 4 and 5 of the periodic table.

The second olefin polymerization catalyst according to the invention mayfurther comprise a carrier (C), in addition to the transition metalcompound (A′) and at least one compound (B) selected from theorganometallic compound (B-1), the organoaluminum oxy-compound (B-2) andthe compound (B-3) which reacts with the transition metal compound (A′)to form an ion pair.

The second process for olefin polymerization comprises polymerizing orcopolymerizing an olefin in the presence of the above-mentioned olefinpolymerization catalyst.

The novel transition metal compound according to the present inventionis represented by the following formula (III):

wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table,

-   -   m is an integer of 1 to 3,    -   R¹ is a hydrocarbon group, a hydrocarbon-substituted silyl        group, a hydrocarbon-substituted siloxy group, an alkoxy group,        an alkylthio group, an aryloxy group, an arylthio group, an        ester group, a thioester group, a sulfonester group or a        hydroxyl group,    -   R² to R⁵ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, a hydrocarbon-substituted silyl group, a        hydrocarbon-substituted siloxy group, an alkoxy group, an        alkylthio group, an aryloxy group, an arylthio group, an ester        group, a thioester group, an amido group, an imido group, an        amino group, an imino group, a sulfonester group, a sulfonamido        group, a cyano group, a nitro group, a carboxyl group, a sulfo        group, a mercapto group or a hydroxyl group,    -   R⁶ is a halogen atom, a hydrocarbon group, a        hydrocarbon-substituted silyl group, a hydrocarbon-substituted        siloxy group, an alkoxy group, an alkylthio group, an aryloxy        group, an arylthio group, an ester group, a thioester group, an        amido group, an imido group, an imino group, a sulfonester        group, a sulfonamido group or a cyano group,    -   two or more of R¹ to R⁶ may be bonded to each other to form a        ring,    -   when m is 2 or greater, two of the groups R¹ to R⁶ may be bonded        to each other, with the proviso that the groups R¹ are not        bonded to each other,    -   n is a number satisfying a valence of M, and    -   X is a halogen atom, a hydrocarbon group, an oxygen-containing        group, a sulfur-containing group, a nitrogen-containing group, a        boron-containing group, an aluminum-containing group, a        phosphorus-containing group, a halogen-containing group, a        heterocyclic compound residue, a silicon-containing group, a        germanium-containing group or a tin-containing group, and when n        is 2 or greater, plural groups X may be the same or different        and may be bonded to each other to form a ring.

The above-mentioned transition metal compound is preferably a compoundrepresented by the following formula (III-a):

wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table,

-   -   m is an integer of 1 to 3,    -   R¹ to R⁵ may be the same or different, and are each a        hydrocarbon group, an alkoxy group or a hydrocarbon-substituted        silyl group,    -   R⁶ is a halogen atom, a hydrocarbon group, a        hydrocarbon-substituted silyl group, an alkoxy group, a        alkylthio group or a cyano group,    -   two or more of R¹ to R⁶ may be bonded to each other to form a        ring,    -   when m is 2 or greater, two groups of the groups R¹ to R⁶ may be        bonded to each other, with the proviso that the groups R¹ are        not bonded to each other,    -   n is a number satisfying a valence of M, and    -   X is a halogen atom, a hydrocarbon group, an oxygen-containing        group, a sulfur-containing group, a nitrogen-containing group, a        halogen-containing group or a silicon-containing group, and when        n is 2 or greater, plural groups X may be the same or different        and may be bonded to each other to form a ring.

In the formula (III-a), m is preferably 2.

The third olefin polymerization catalyst according to the presentinvention comprises:

-   -   (A″) a novel transition metal compound as described above, and    -   (B) at least one compound selected from:        -   (B-1) an organometallic compound,        -   (B-2) an organoaluminum oxy-compound, and        -   (B-3) a compound which reacts with the transition metal            compound (A) to form an ion pair.

The third olefin polymerization catalyst according to the presentinvention may further comprise a carrier (C) in addition to thetransition metal compound (A″) and at least one compound (B) selectedfrom the organometallic compound (B-1), the organoaluminum oxy-compound(B-2) and the compound (B-3) which reacts with the transition metalcompound (A″) to form an ion pair.

The third process for olefin polymerization comprises polymerizing orcopolymerizing an olefin in the presence of the above-mentioned olefinpolymerization catalyst.

The α-olefin/conjugated diene copolymer according to the presentinvention is an α-olefin/conjugated diene copolymer having a molecularweight distribution (Mw/Mn) of not more than 3.5, a content ofconstituent units derived from an α-olefin in the range of 1 to 99.9% bymol and a content of constituent units derived from a conjugated dienein the range of 99 to 0.1% by mol, in which the polymer chain contains1,2-cyclopentane skeleton derived from the conjugated diene in an amountof not more than 1% by mol, and preferably the polymer chain does notsubstantially contain the 1,2-cyclopentane skeleton.

In the α-olefin/conjugated diene copolymer according to the invention,it is preferred that the content of the constituent units derived fromthe α-olefin is in the range of 50 to 99.9% by mol and the content ofthe constituent units derived from the conjugated diene is in the rangeof 50 to 0.1% by mol.

In the α-olefin/conjugated diene copolymer according to the invention,it is preferred that the α-olefin is ethylene and/or propylene and theconjugated diene is butadiene and/or isoprene.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows steps for preparing the first olefin polymerizationcatalyst according to the invention.

FIG. 2 shows steps for preparing the second olefin polymerizationcatalyst according to the invention.

FIG. 3 shows the structure of transition metal compound A-1 prepared inSynthesis Example 1, which was determined by X-ray structure analysis.

FIG. 4 shows the structure of transition metal compound B-1 prepared inSynthesis Example 2, which was determined by X-ray crystal structureanalysis.

DETAILED DESCRIPTION OF THE INVENTION

The olefin polymerization catalyst of the present invention and theprocess for olefin polymerization using the catalyst are described indetail hereinafter.

The meaning of the term “polymerization” used herein is not limited to“homopolymerization” but may comprehend “copolymerization”. Also, themeaning of the term “polymer” used herein is not limited to“homopolymer” but may comprehend “copolymer”.

First Olefin Polymerization Catalyst

The first olefin polymerization catalyst of the invention is formedfrom:

-   -   (A) a transition metal compound represented by the        below-described formula (I), and    -   (B) at least one compound selected from:        -   (B-1) an organometallic compound,        -   (B-2) an organoaluminum oxy-compound, and        -   (B-3) a compound which reacts with the transition metal            compound (A) to form an ion pair.

First, the catalyst components for forming the olefin polymerizationcatalyst of the invention are described.

(A) Transition Metal Compound

The transition metal compound (A) for use in the invention is a compoundrepresented by the following formula (I).

In the formula (I), M is a transition metal atom of Group 3 to Group 11of the periodic table (Group 3 includes lantanoids), preferably Groups 3to 9 (Group 3 includes lantanoids), more preferably Group 3 to Group 5and Group 9, and particularly preferably Groups 4 or 5. SpecificExamples of transition metal atoms M include scandium, titanium,zirconium, hafnium, vanadium, niobium, tanthalum, cobalt, rhodium,yttriumn, chromium, molybdenum, tungsten, mangafese, rhenium, iron andruthenium. Of these, preferred are scandium, titanium, zirconium,hafnium, vanadium, niobium, tanthalum, cobalt and rhodium; morepreferred are titanium, zirconium, hafnium, vanadium, niobium,tanthalum, cobalt and rhodium; and particularly preferred are titanium,zirconium and hafnium.

m is an integer of 1 to 6, preferably 1 to 4.

R¹ to R⁶ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group, a heterocyclic compound residue, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group, and two or more of them may be bonded to eachother to form a ring,

The halogen atom is fluorine, chlorine, bromine or iodine.

Examples of the hydrocarbon groups include straight-chain or branchedalkyl groups of 1 to 30, preferably 1 to 20 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, neopentyl and n-hexyl;

-   -   straight-chain or branched alkenyl groups of 2 to 30, preferably        2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl;    -   straight-chain or branched alkynyl groups of 2 to 30, preferably        2 to 20 carbon atoms, such as ethynyl and propargyl;    -   cyclic saturated hydrocarbon groups of 3 to 30, preferably 3 to        20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl and adamantyl;    -   cyclic unsaturated hydrocarbon groups of 5 to 30, preferably 5        to 20 carbon atoms, such as cyclopentadienyl, indenyl and        fluorenyl; and    -   aryl groups of 6 to 30, preferably 6 to 20 carbon atoms, such as        phenyl, benzyl, naphthyl, biphenyl and terphenyl.

The hydrocarbon groups may be substituted with halogen atoms and forsuch examples halogenated hydrocarbon groups of 1 to 30, preferably 1 to20 carbon atoms, such as trifluoromethyl, pentafluorophenyl andcholophenyl may be mentioned.

The hydrocarbon groups may also be substituted with other hydrocarbongroups and for such examples aryl-substituted alkyl groups such asbenzyl and cumyl may be mentioned.

Further, the hydrocarbon groups may have heterocyclic compound residues;oxygen-containing groups such as alkoxy, aryl, ester, ether, acyl,carboxyl, carbonato, hydroxy, peroxy and carboxylic acid anhydridegroups; nitrogen-containing groups such as ammonium salts of amino,imino, amide, imide, hydrazino, hydrazono, nitro, nitroso, cyano,isocyano, cyanic acid ester, amidino and diazo groups; boron-containinggroups such as borandiyl, borantriyl and diboranyl groups;sulfur-containing groups such as mercapto, thioester, dithioester,alkylthio, arylthio, thioacyl, thioether, thiocyanic acid ester,isothiocyanic acid ester, sulfon ester, sulfon amide, thiocarboxyl,dithiocarboxyl, sulfo, sulfonyl, sulfinyl and sulfenyl groups;phosphorus-containing groups such as phosphido, phosphoryl,thiophosphoryl and phosphato groups; silicon-containing groups;germanium-containing groups; and tin-containing groups.

Of these, particularly preferable are straight-chain or branched alkylgroups of 1 to 30, preferably 1 to 20 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,neopentyl and n-hexyl; aryl groups of 6 to 30, preferably 6 to 20 carbonatoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl andantracenyl; and these aryl groups which are substituted with 1 to 5substituents such as alkyl or arkoxy groups of 1 to 30, preferably 1 to20 carbon atoms, aryl or aryloxy groups of 6 to 30, preferably 6 to 20carbon atoms.

Examples of nitrogen-containing groups, boron-containing groups,sulfur-containing groups and phosphorus-containing groups are thoseexemplified above.

Examples of the heterocyclic residues include those ofnitrogen-containing compounds (e.g., pyrrole, pyridine, pyrimidine,quinoline and triazine), oxygen-containing compounds (e.g., furan andpyran) and sulfur-containing compounds (e.g., thiophene), and theseheterocyclic residues, which are substituted with substituents such asalkyl or alkoxy groups of 1 to 20 carbon atoms.

Examples of the silicon-containing groups include silyl, siloxy,hydrocarbon-substituted silyl groups such as methylsilyl, dimethylsilyl,trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl,diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl,dimethyl-t-butylsilyl and dimethyl(pentafluorophenyl)silyl, preferablymethylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl,triethylsilyl and triphenylsilyl, particularly preferablytrimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl,and hydrocarbon-substituted siloxy groups such as trimethylsiloxy.

The germanium-containing groups and the tin-containing groups includethe above-mentioned silicon-containing groups in which silicon isreplaced by germanium and tin, respectively.

The more specific illustration on the above R¹ to R⁶ is given below.

Examples of the alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy and tert-butoxy.

Examples of the alkylthio groups include methylthio and ethylthio.

Examples of the aryloxy groups include phenoxy, 2,6-dimethylphenoxy and2,4,6-trimethylphenoxy.

Examples of the arylthio groups include phenylthio, methylphenylthio andnaphthylthio.

Examples of the acyl groups include formyl, acyl, benzoyl,p-chlorobenzoyl and p-methoxybenzoyl.

Examples of the ester groups include acetyloxy, benzoyloxy,methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

Examples of the thioester groups include acetylthio, benzoylthio,methylthiocarbonyl and phenylthiocarbonyl.

Examples of the amido groups include acetamido, N-methylacetamido andN-methylbenzamido.

Examples of the imido groups include acetimido and benzimido.

Examples of the amino groups include dimethylamino, ethylmethylamino anddiphenylamino.

Examples of the imino groups include methylimino, ethylimino,propylimino, butylimino and phenylimino.

Examples of the sulfonester groups include methylsulfonato,ethylsulfonato and phenylsulfonato.

Examples of the sulfonamido groups include phenylsulfonamido,N-methylsulfonamido and N-methyl-p-toluenesulfonamido.

R⁶ is preferably a substituent other than hydrogen. That is, a hydrogenatom, a halogen atom, a hydrocarbon group, a heterocyclic compoundresidue, an oxygen-containing group, a nitrogen-containing group, aboron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring. R⁶ is particularlypreferably a halogen atom, a hydrocarbon group, a heterocyclic compoundresidual group, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group.

Preferred examples of the hydrocarbon groups available as R⁶ includestraight-chain or branched alkyl groups of 1 to 30, preferably 1 to 20carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, neopentyl and n-hexyl; cyclic saturatedhydrocarbon groups of 3 to 30, preferably 3 to 20 carbon atoms, such ascyclopropanyl, cyclobutanyl, cyclopentanyl, cyclohexyl and adamantyl;aryl groups of 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl,benzyl, naphthyl, biphenyl and terphenyl; and these groups which aresubstituted with substituents such as alkyl or alkoxy groups of 1 to 30,preferably 1 to 20 carbon atoms, halogenated alkyl groups of 1 to 30,preferably 1 to 20 carbon atoms, aryl or alkoxy groups of 6 to 30,preferably 6 to 20 carbon atoms, halogen, cyano, nitro and hydroxyl.

Preferred examples of the hydrocarbon-substituted silyl groups as R⁶include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl anddimethyl(pentafluorophenyl)silyl. Particularly preferable aretrimethylsilyl, triphenylsilyl, diphenylmethylsilyl, isophenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl anddimethyl(pentafluorophenyl)silyl.

In the present invention, R⁶ is a preferably selected from branchedalkyl groups of 3 to 30, preferably 3 to 20 carbon atoms (e.g.,isopropyl, isobutyl, sec-butyl and tert-butyl neopentyl), these alkylgroups which are substituted with aryl groups of 6 to 30, preferably 6to 20 carbon atoms (e.g., cumyl), and cyclic saturated hydrocarbongroups of 3 to 30, preferably 3 to 20 carbon atoms (e.g., adamantyl,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl).

Also, preferable R⁶ is an aryl group of 6 to 30, preferably 6 to 20carbon atoms (e.g., phenyl, naphthyl, fluorenyl, anthranyl orphenanthryl) or a hydrocarbon-substituted silyl group.

Two or more of the groups R¹ to R⁶, preferably adjacent groups, may bebonded to each other to form an aliphatic ring, an aromatic ring or ahydrocarbon ring containing a hetero atom such as a nitrogen atom, andthese rings may further have a substituent.

When m is 2 or greater, two of the groups R¹ to R⁶ may be bonded to eachother, with the proviso that the groups R¹ are not bonded to each other.R¹s, R²s, R³s, R⁴s, R⁵s, or R⁶s may be the same as or different fromeach other.

n is a number satisfying a valence of M, specifically an integer of 0 to5, preferably 1 to 4, mroe preferably 1 to 3.

X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine andiodine.

Examples of the hydrocarbon groups include those exemplified for R¹ toR⁶. Specifically, there can be mentioned, but not limited to, alkylgroups, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl,dodecyl and eicosyl; cycloalkyl groups of 3 to 30 carbon atoms, such ascyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups, suchas vinyl, propenyl and cyclohexenyl; arylalkyl groups, such as benzyl,phenylethyl and phenylpropyl; and aryl groups, such as phenyl, tolyl,dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,naphthyl, methylnaphthyl, anthryl and phenanthryl.

These hydrocarbon groups include halogenated hydrocarbon groups, andmore specifically at least one hydrogen of the hydrocarbon groups of 1to 30 carbon atoms may be substituted with a halogen atom.

Of these, preferable are those of 1 to 20 carbon atoms.

Examples of the heterocyclic compound residues include those exemplifiedfor R¹ to R⁶.

Examples of the oxygen-containing groups include those exemplified forR¹ to R⁶. Specificatlly, there can be mentioned, but not limited to,hydroxyl; alkoxy groups, such as methoxy, ethoxy, propoxy and butoxy;aryloxy groups, such as phenoxy, methylphenoxy, dimethylphenoxy andnaphthoxy; arylalkoxy groups, such as phenylmethoxy and phenylethoxy;acetoxy groups; and carbonyl group.

Examples of the sulfur-containing groups include those exemplified forR¹ to R⁶. Specifically, there can be mentioned, but not limited to,sulfonato groups, such as methylsulfonato, trifluoromethanesulfonato,phenylsulfonato, benzylsulfonato, p-toluenesulfonato,trimethylbenzenesulfonato, triisobutylbenzenesulfonato,p-chlorobenzenesulfonato and pentafluorobenzenesulfonato; sulfinatogroups, such as methylsulfinato, phenylsulfinato, benzylsulfinato,p-toluenesulfinato, trimethylbenzenesulfinato andpentafluorobenzenesulfinato; alkylthio groups; and arylthio groups.

Examples of the nitrogen-containing groups include those exemplified forR¹ to R⁶. Specifically, there can be mentioned, but not limited to,amino group; alkylamino groups, such as methyl amino, dimethylamino;diethylamino; dipropylamino, dibutylamino and dicyclohexylamino;arylamino groups and alkylarylamino groups, such as phenylamino,diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino.

Examples of the boron-containing groups include BR₄ groups (where R is ahydrogen, an aryl group which may have a substituent, a halogen, etc.).

Examples of the silicon-containing groups include those exemplified forR¹ to R⁶. Specifically, there can be mentioned, but not limited to,hydrocarbon-substituted silyl groups, such as phenylsilyl,diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl,tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyland trinaphthylsilyl; hydrocarbon-substituted silylether groups, such astrimethylsilylether; silicon-substituted alkyl groups, such astrimethylsilylmethyl; and silicon-substituted aryl groups, such astrimethylsilylphenyl.

Examples of the germanium-containing groups include those exemplifiedfor R¹ to R⁶. Specifically, there can be mentioned the above-mentionedsilicon-containing groups in which silicon is replaced by germanium.

Examples of the tin-containing groups include those exemplified for R¹to R⁶. Specifically, there can be mentioned the above-mentionedsilicon-containing groups in which silicon is replaced by tin.

Examples of the halogen-containing groups include fluorine-containinggroups, such as PF₆ and BF₄; chlorine-containing groups, such as ClO₄and SbCl₆; and iodine-containing groups, such as IO₄, but not limitedthereto.

Examples of the aluminium-containing groups include AR₄ groups (where Ris a hydrogen, an alkyl group, an aryl group which may have asubstituent, a halogen atom, etc.), but not limited thereto.

When n is 2 or greater, plural groups X may be the same or different andmay be bonded to each other to form a ring.

Transition Metal Compound (I-a)

The transition compound represented by the formula (I) is preferably acompound represented by the formula (I-a).

In the formula (I-a), M is a transition metal atom of Group 3 to Group11 of the periodic table. Examples of M include the above-mentionedtransition metal atoms.

m is an integer of 1 to 3, preferably 2.

R¹ to R⁶ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group, a heterocyclic compound residues, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an acyl group, an ester group, a thioester group, anamido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group, acaroboxyl group, a sulfo group, a mercapto group or a hydroxyl group,and two or more of them may be bonded to each other to form a ring.Examples of R¹ to R⁶ include those described above.

When m is 2 or greater, two of the groups R¹ to R⁶ may be bonded to eachother, with the proviso that the groups R¹ are not bonded to each other.

n is a number satisfying a valence of M, specifically an integer of 0 to5, preferably 1 to 4, more preferably 1 to 3.

X is a hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group. Examples of X include those described above.

When n is 2 or greater, plural groups X may be the same or different andmay be bonded to each other to form a ring.

The transition metal compound represented by the formula (I) ispreferably a compound represented by the following formula (I-a-1).

In the formula (I-a-1), R¹ to R⁶, M and X have the same meanings asmentioned above, and are preferably those described below.

M is a transition metal atom of Group 3 to Group 11 of the periodictable, preferably of Group 3 to Group 5 and Group 9, e.g., scandium,titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt orrhodium, more preferably titanium, zirconium, hafnium, cobalt orrhodium, particularly preferably titanium, zirconium or hafnium.

m is an integer of 1 to 3.

R¹ to R⁶ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group, a heterocyclic compound residues, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, a thioester group, an ester group, an acyl group, anamido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group ora hydroxyl group. Of these, particularly preferable is a hydrogen atom,a halogen atom, a hydrocarbon-substituted silyl group, an alkoxy group,an aryloxy group, an ester group, an amido group, an amino group, asulfonamido group, a cyano group or a nitro group.

Examples of the halogen atom include fluorine, chlorine, bromine andiodine.

Examples of the hydrocarbon groups include straight-chain or branchedalkyl groups of 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl;straight-chain or branched alkenyl groups of 2 to 20 carbon atoms, suchas vinyl, allyl and isopropenyl; straight-chain or branched alkynylgroups of 2 to 20 carbon atoms, such as ethynyl and propargyl; cyclicsaturated hydrocarbon groups of 3 to 20 carbon atoms, such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; arylgroups of 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl,biphenylyl and triphenylyl; cyclic unsaturated hydrocarbon groups of 5to 20 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl; andthese groups which are substituted with substituents such as alkylgroups of 1 to 20 carbon atoms, halogenated alkyl groups of 1 to 20carbon atoms, aryl groups of 6 to 20 carbon atoms, alkoxy groups of 1 to20 carbon atoms, aryloxy groups of 6 to 20 carbon atoms, halogen, cyano,nitro and hydroxyl. Of these, particularly preferable are straight-chainor branched alkyl groups of 1 to 20 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyland hexyl; aryl groups of 6 to 20 carbon atoms, such as phenyl andnaphthyl; and these aryl groups which are substituted with 1 to 5substituents such as alkyl groups of 1 to 20 carbon atoms, aryl groupsof 6 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms andaryloxy groups of 6 to 20 carbon atoms.

Examples of the heterocyclic residues include residues ofnitrogen-containing compounds (e.g., pyrrole, pyridine, pyrimidine,quinoline and triazine), oxygen-containing compounds (e.g., furan andpyran) and sulfur-containing compounds (e.g., thiophene), and theseheterocyclic residues which are substituted with substituents such asalkyl groups and alkoxy groups fo 1 to 20 carbon atoms.

Examples of the hydrocarbon-substituted silyl groups includemethylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl,triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl,dimethyl-t-butylsilyl and dimethyl(pentafluorophenyl)silyl. Of these,particularly preferable are methylsilyl, dimethylsilyl, trimethylsilyl,ethylsilyl, diethylsilyl, triethylsilyl and triphenylsilyl.

Examples of the hydrocarbon-substituted siloxy groups includetrimethylsiloxy.

Examples of the alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy and tert-butoxy.

Examples of the alkylthio groups include methylthio and ethylthio.

Examples of the aryloxy groups include phenoxy, 2,6-dimethylphenoxy and2,4,6-trimethylphenoxy.

Examples of the arylthio groups include phenylthio, methylphenylthio andnaphthylthio.

Examples of the acyl groups include formyl, acetyl, benzoyl,p-chlorobenzoyl and p-methoxybenzoyl.

Examples of the ester groups include acetyloxy, benzoyloxy,methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

Examples of the thioester groups include acetylthio, benzoylthio,methylthiocarbonyl and phenylthiocarbonyl.

Examples of the amido groups include acetamido, N-methylacetamido andN-methylbenzamido.

Examples of the imido groups include acetimido and benzimido.

Examples of the amino groups include dimethylamino, ethylmethylamino anddiphenylamino.

Examples of the imino groups include methylimino, ethylimino,propylimino, butylimino and phenylimino.

Examples of the sulfonester groups include methylsulfonato,ethylsulfonato and phenylsulfonato.

Examples of the sulfonamido groups include phenylsulfonamido,N-methylsulfonamido and N-methyl-p-toluenesulfonamido.

R⁶ is preferably a substituent other than hydrogen. That is, R⁶ ispreferably a halogen atom, a hydrocarbon group, a heterocyclic compoundresidues, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an acyl group, an estergroup, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group.

Preferred examples of the hydrocarbon groups as R⁶ includestraight-chain or branched alkyl groups of 1 to 20 carbon atoms, such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl and hexyl; cyclic saturated hydrocarbon groups of 3to 20 carbon atoms, such as cyclopropyl, cyclobutnyl, cyclopentyl,cyclohexyl and adamantyl; aryl groups of 6 to 20 carbon atoms, such asphenyl, benzyl, naphthyl, biphenylyl and triphenylyl; and these groupswhich are substituted with substituents such as alkyl groups of 1 to 20carbon atoms, halogenated alkyl groups of 1 to 20 carbon atoms, arylgroups of 6 to 20 carbon atoms, alkoxy groups of 1 to 20 carbon atoms,aryloxy groups of 6 to 20 carbon atoms, halogen, cyano, nitro andhydroxyl.

Preferred examples of the hydrocarbon-substituted silyl groups as R⁶include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,dimethylphenylsilyl, dimethyl-t-butylsilyl anddimethyl(pentafluorophenyl)silyl.

In the present invention, R⁶ is preferably selected from branched alkylgroups of 3 to 20 carbon atoms (e.g., isopropyl, isobutyl, sec-butyl andtert-butyl), these alkyl groups which are substituted with aryl groupsof 6 to 20 carbon atoms (e.g., cumyl), and cyclic saturated hydrocarbongroups of 3 to 20 carbon atoms (e.g., adamantyl, cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl). Also, preferable R⁶ is ahydrocarbon-substituted silyl group.

Two or more groups R¹ to R⁶, preferably adjacent groups, may be bondedto each other to form an aliphatic ring, an aromatic ring or ahydrocarbon ring containing a hetero atom such as a nitrogen atom, andthese rings may further have a substituent.

When m is 2 or greater, two of the the groups R¹ to R⁶ may be bonded toeach other, with the proviso that the groups R¹ are not bonded to eachother. R¹s, R²s, R³s, R⁴s, R⁵s, or R⁶s may be the same as or differentfrom each other.

n is a number satisfying a valence of M, specifically an integer of 1 to3.

X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group or asilicon-containing group, and when n is 2 or greater, plural groups Xmay be the same or different.

Examples of the he halogen atoms include fluorine, chlorine, bromine andiodine.

Examples of the hydrocarbon groups of 1 to 20 carbon atoms include alkylgroups, cycloalkyl groups, alkenyl groups, arylalkyl groups and arylgroups. Specifically, there can be mentioned alkyl groups, such asmethyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl;cycloalkyl groups, such as cyclopentyl, cyclohexyl, norbornyl andadamantyl; alkenyl groups, such as vinyl, propenyl and cyclohexenyl;arylalkyl groups, such as benzyl, phenylethyl and phenylpropyl; and arylgroups, such as phenyl, tolyl, dimethylphenyl, trimethylphenyl,ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryland phenanthryl.

Examples of the halogenated hydrocarbon groups of 1 to 20 carbon atomsinclude the above-mentioned hydrocarbon groups of 1 to 20 carbon atomswhich are substituted with halogens.

Examples of the oxygen-containing groups include hydroxyl; alkoxygroups, such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups,such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; andarylalkoxy groups, such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing groups include the above-exemplifiedoxygen-containing groups in which oxygen is replaced with sulfur;sulfonato groups, such as methylsulfonato, trifluoromethanesulfonato,phenylsulfonato, benzylsulfonato, p-toluenesulfonato,trimethylbenzenesulfonato, triisobutylbenzenesulfonato,p-chlorobenzenesulfonato and pentafluorobenzenesulfonato; and sulfinatogroups, such as methylsulfinato, phenylsulfinato, benzylsulfinato,p-toluenesulfinato, trimethylbenzenesulfinato andpentafluorobenzenesulfinato.

Examples of the silicon-containing groups includemonohydrocarbon-substituted silyl groups, such as methylsilyl andphenylsilyl; dihydrocarbon-substituted silyl groups, such asdimethylsilyl and diphenylsilyl; trihydrocarbon-substituted silylgroups, such as trimethylsilyl, triethylsilyl, tripropylsilyl,tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl,methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethergroups of hydrocarbon-substituted silyl, such as trimethylsilyl ether;silicon-substituted alkyl groups, such as trimethylsilylmethyl; andsilicon-substituted aryl groups, such as trimethylsilylphenyl.

Of these, preferable groups X are halogen atoms, hydrocarbon atoms of 1to 20 carbon atoms and sulfonato groups.

When n is 2 or greater, groups X may be bonded to each other to form aring.

Of the transition metal compounds represented by the formula (I-a-1),the compound wherein m is 2 and two of the groups R¹ to R⁶ (except forthe groups R¹) are bonded to each other is, for example, a compoundrepresented by the following formula (I-a-2).

In the formula (I-a-2), M, R¹ to R⁶, and X are identical with M, R¹ toR⁶, and X in the formula (I).

R¹ to R¹⁶ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group, a heterocyclic compound residue, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an acyl group, an ester group, a thioester group, anamido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group or a nitro group,specifically, the same atom or group as described for R¹ to R⁶. Two ormore of groups R¹ to R¹⁶, preferably adjacent groups, may be bonded toeach other to form an aliphatic ring, an aromatic ring or a hydrocarbonring containing a hetero atom such as a nitrogen atom.

Y′ is a bonding group or a single bond for bonding at least one groupselected from R¹ to R⁶ to at least one group selected from R¹¹ to R¹⁶(except a case of bonding R¹ and R¹¹ to each other).

The bonding group Y′ is a group containing at least one element selectedfrom among oxygen, sulfur, carbon, nitrogen, phosphorus, silicon,selenium, tin, boron and the like. Examples of such groups includegroups containing chalcogen atoms such as —O—, —S— and —Se—; nitrogen-or phosphorus-containing groups, such as —NH—, —N(CH₃)₂, —PH— and—P(CH₃)₂—; hydrocarbon groups of 1 to 20 carbon atoms, such as —CH₂—,—CH₂—CH₂— and —C(CH₃)₂—; residues of cyclic unsaturated hydrocarbons of6 to 20 carbon atoms, such as benzene, naphthalene and anthracene;residues of heterocyclic compounds having 3 to 20 carbon atoms andcontaining hetero atoms, such as pyridine, quinoline, thiophene andfuran; silicon atom-containing groups, such as —SiH₂— and —Si(CH₃)₂; tinatom-containing groups, such as —SnH₂— and —Sn(CH₃)₂; and boronatom-containing groups, such as —BH—, —B(CH₃)— and —BF—.

Examples of the transition metal compounds represented by the formula(I-a-1) are given below, but are not limited thereto.

In the following examples, M is a transition metallic element, andspecifically represents, but not limited to, Sc(III), Ti(III), Ti(IV),Zr(III), Zr(IV), Hf(IV), V(IV), Nb(V), Ta(V), Co(II), Co(III), Rh(II),Ph(III), Ph(IV). Of these, particularly preferable is Ti(IV), Zr(IV) orHf(IV).

X is halogen such as Cl or Br, or an alkyl group such as methyl, but notlimited thereto. When plural X are present, they may be the same ordifferent.

n depends on a valence of the metal M. For example, when two monoanionspecies are bonded to the metal, n=0 in case of a divalent metal, n=1 incase of a trivalent metal, n=2 in case of a tetravalent metal, and n=3in case of a pentavalent metal. More specifically, there can bementioned n=2 in case of Ti(IV), n=2 in case of Zr(IV), and n=2 in caseof Hf(IV).

In the above chemical formulae, Me is methyl, Et is ethyl, iPr isisopropyl, tBu is tert-butyl and Ph is phenyl.

More specific examples of compounds having a center metal Ti are givenbelow. There can also be mentioned those compounds in which titanium isreplaced with zirconium, hafnium, cobalt or rhodium.

In the olefin polymerization catalyst according to the invention, it isparticularly preferable to use a novel transition metal compound of theformula (III), which will be described in detail below, as the catalystcomponent (A′).

Transition Metal Compound (I-b)

Also employable as the transition metal compound (A) in the invention isa transition metal compound represented by the following formula (I-b).

In the formula (I-b), M is a transition metal atom of Group 3 to Group11 of the periodic table, preferably of Group 4 or Group 9, andparticularly preferably, titanium, zirconium, hafnium, cobalt orrhodium.

m is an integer of 1 to 6, preferably 1 to 4.

R¹ to R⁶ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group, a hydrocarbon-substituted silylgroup, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup.

of these, particularly preferable is a halogen atom, a hydrocarbongroup, a hydrocarbon-substituted silyl group, an alkoxy group, anaryloxy group, an ester group, an amido group, an amino group, asulfonamido group, a cyano group or a nitro group.

Examples of the groups R¹ to R⁶ are those exemplified for the transitionmetal compounds of the formulae (I) and (I-a).

When m is 2 or greater, two or more groups R¹ to R⁶, preferably adjacentgroups, may be bonded to each other to form a ring, with the provisothat the groups R¹ are not bonded to each other.

Examples of the transition metal compounds represented by the formula(I-b) are given below, but not limited thereto.

In the present invention, transition metal compounds wherein cobalt isreplaced with titanium, zirconium, hafnium, iron, copper or rhodium inthe above-exemplified compounds are also employable.

The transition metal compounds (A) mentioned above are used singly or incombination of two or more kinds, and they can be used in combinationwith other transition metal compounds, for example known transitionmetal compounds comprising a ligand which has a hetero atom such asnitrogen, oxygen, sulfur, boron or phosphorus.

Other Transition Metal Compound

Some examples of the other transition metal compounds are given below,but the compounds are not limited those examples.

(a-1) Transition Metal Imide Compound (I-c)

In the above formula, M is a transition metal atom of Group 8 to Group10 of the periodic table, preferably nickel, palladium or platinum.

R²¹ to R²⁴ may be the same or different, and are each a hydrocarbongroup of 1 to 50 carbon atoms, a halogenated hydrocarbon group of 1 to50 carbon atoms, a hydrocarbon-substituted silyl group, or a hydrocarbongroup substituted with a substituent containing at least one elementselected from nitrogen, oxygen, phosphorus, sulfur and silicon.

Two or more groups, preferably adjacent groups, of R²¹ to R²⁴ may bebonded to each other to form a ring.

q is an integer of 0 to 4.

X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group, and when q is 2or greater, plural groups X may be the same or different.

(a-2) Transition Metal Amide Compound (I-d)

In the above formula, M is a transition metal atom of Group 3 to Group 6of the periodic table, preferably titanium, zirconium or hafnium.

R′ and R″ may be the same or different, and are each a hydrogen atom, ahydrocarbon group of 1 to 50 carbon atoms, a halogenated hydrocarbongroup of 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, ora substituent containing at least one element selected from nitrogen,oxygen, phosphorus, sulfur and silicon.

m is an integer of 0 to 2.

n is an integer of 1 to 5.

A is an atom of Group 13 to Group 16 of the periodic table, specificallyboron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium,selenium, tin or the like, preferably carbon or silicon.

When n is 2 or greater, plural atoms A may be the same or different.

E is a substituent containing at least one element selected from carbon,hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron andsilicon. When plural groups E are present, they may be the same ordifferent, and two or more groups E may be bonded to form a ring.

p is an integer of 0 to 4.

X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group. When p is 2 orgreater, plural groups X may be the same or different.

X is preferably a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms or a sulfonato group.

(a-3) Transition Metal Diphenoxy Compound (I-e)

In the above formula, M is a transition metal atom of Group 3 to Group11 of the periodic table; 1 and m are each an integer of 0 or 1; A andA′ are each a hydrocarbon group of 1 to 50 carbon atoms, a halogenatedhydrocarbon group of 1 to 50 carbon atoms, a hydrocarbon group having asubstituent containing oxygen, sulfur or silicon, or a halogenatedhydrocarbon group having a substituent containing oxygen, sulfur orsilicon; and A and A′ may be the same or different.

B is a hydrocarbon group of 0 to 50 carbon atoms, a halogenatedhydrocarbon group of 1 to 50 carbon atoms, R¹R²Z, oxygen or sulfur,where R¹ and R² are each a hydrocarbon group of 1 to 20 carbon atoms ora hydrocarbon group having 1 to 20 carbon atoms and containing at leastone hetero atom, and Z is carbon, nitrogen, sulfur, phosphorus orsilicon.

n is a number satisfying a valence of M.

X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group, and when n is 2or greater, plural groups X may the same or different and may be bondedto form a ring.

(a-4) Transition Metal Compound (I-f) Containing at Least One HeteroAtom and Containing a Ligand Having Cyclopentadienyl Skeleton

In the above formula, M is a transition metal atom of Group 3 to Group11 of the periodic table. X is an atom of Group 13, Group 14 or Group15, and at least one of X contains an element other than carbon.

Each R may be the same or different, and is a hydrogen atom, a halogenatom, a hydrocarbon group, a halogenated hydrocarbon group, ahydrocarbon-substituted silyl group or a hydrocarbon group substitutedwith a substituent containing at least one element selected fromnitrogen, oxygen, phosphorus, sulfur and silicon. Two or more of R maybe bonded to form a ring, and a is 0 or 1.

b is an integer of 1 to 4, when b is a number of 2 or greater, themoieties [((R)_(a))₅X₅] may be the same or different, and the groups Rmay be bonded to form a bridge.

c is a number satisfying a valence of M.

Y is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group, asilicon-containing group, or nitrogen-containing group. When c is anumber of 2 or greater, plural groups Y may be the same or different andmay be bonded to form a ring.

(a-5) Transition Metal Compound Represented by the Formula RB(Pz)₃MX_(n)

In the above formula, M is a transition metal atom of Group 3 to Group11 of the periodic table; R is a hydrogen atom, a hydrocarbon group of 1to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbonatoms; and Pz is a pyrazolyl group or a substituted pyrazolyl group.

n is a number satisfying a valence of M.

X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or nitrogen-containing group, and when n is anumber of 2 or greater, plural groups X may be the same or different andmay be bonded to form a ring.

(a-6) Transition Metal Compound Represented by the Following Formula(I-g)

In the above formula, Y₁ and Y₃ are each an element of Group 15 of theperiodic table; Y₂ is an element of Group 16 of the periodic table; andR²¹ to R²⁸ may be the same or different, they are each a hydrogen atom,a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, ahalogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing group, a sulfur-containing group or asilicon-containing group, and two or more of them may be bonded to forma ring.

(a-7) Transition Metal Compound Comprising a Compound Represented by theFollowing Formula (I-h) and a Transition Metal Atom of Group VIII

In the above formula, R³¹ to R³⁴ may be the same or different, they areeach a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms,and two or more of them may be bonded to form a ring.

(a-8) Transition Metal Compound Represented by the Following Formula(I-i)

In the above formula, M is a transition metal atom of Group 3 to Group11 of the periodic table.

m is an integer of 0 to 3.

n is an integer of 0 or 1.

p is an integer of 1 to 3.

q is a number satisfying a valence of M.

R⁴¹ to R⁴⁸ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing group, a sulfur-containing group, a silicon-containinggroup or nitrogen-containing group, and two or more of them may bebonded to form a ring.

X is a hydrogen atom, a hologen atom, a hydrocarbon group of 1 to 20carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms,an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group, and when q is 2or greater, plural X may be the same or different and may be bonded toeach other to form a ring.

Y is a group bridging the borata benzen ring, and Y is carbon, siliconor germanium.

A is an element of Group 14, Group 15 or Group 16 of the periodic table.

(B-1) Organometallic Compound

As the organometallic compound (B-1), the below-described organometalliccompounds of metals of Group 1, Group 2, Group 12 and Group 13 of theperiodic table are employable in the invention.

-   -   (B-1a) Organoaluminum compound represented by the following        formula:        R^(a) _(m)Al(OR^(b))_(n)H_(p)X_(q)        wherein R^(a) and R^(b) may be the same or different, and are        each a hydrocarbon group of 1 to 15 carbon atoms, preferably a        hydrocarbon group of 1 to 4 carbon atoms; X is a halogen atom;        and m, n, p and q are numbers satisfying the conditions of        0<m≦3, 0≦n<3, 0≦p<3, 0≦q<3 and m+n+p+q=3.    -   (B-1b) Alkyl complex compound of Group 1 metal and aluminum,        that is represented by the following formula:        M²AlR^(a) ₄        wherein M² is Li, Na or K; and R^(a) is a hydrocarbon group of 1        to 15 carbon atoms, preferably a hydrocarbon group of 1 to 4        carbon atoms.    -   (B-1c) Dialkyl compound of Group 2 metal or Group 12 metal, that        is represented by the following formula:        R^(a)R^(b)M³        wherein R^(a) and R^(b) may be the same or different, and are        each a hydrocarbon group of 1 to 15 carbon atoms, preferably a        hydrocarbon group of 1 to 4 carbon atoms; and M³ is Mg, Zn or        Cd.

Examples of the organoaluminum compounds (B-1a) include the followingcompounds.

-   -   organoaluminum compound represented by the following formula:        R^(a) _(m)Al(OR^(b))_(3-m)        wherein R^(a) and R^(b) may be the same or different, and are        each a hydrocarbon group of 1 to 15 carbon atoms, preferably a        hydrocarbon group of 1 to 4 carbon atoms; and m is preferably a        number satisfying the condition of 1.5≦m≦3.    -   Organoaluminum compound represented by the following formula:        R^(a) _(m)AlX_(3-m)        wherein R^(a) is a hydrocarbon group of 1 to 15 carbon atoms,        preferably a hydrocarbon group of 1 to 4 carbon atoms; X is a        halogen atom; and m is preferably a number satisfying the        condition of 0<m<3.    -   Organoaluminum compound represented by the following formula:        R^(a) _(m)AlH_(3-m)        wherein R^(a) is a hydrocarbon group of 1 to 15 carbon atoms,        preferably a hydrocarbon group of 1 to 4 carbon atoms; and m is        preferably a number satisfying the condition of 2≦m<3.    -   Organoaluminum compound represented by the following formula:        R^(a) _(m)Al(OR^(b))_(n)X_(q)        wherein R^(a) and R^(b) may be the same or different, and are        each a hydrocarbon group of 1 to 15 carbon atoms, preferably a        hydrocarbon group of 1 to 4 carbon atoms; X is a halogen atom;        and m, n and q are numbers satisfying the conditions of 0<m≦3,        0≦n<3, 0≦q<3 and m+n+q=3.

Particular examples of the organoaluminum compounds (B-1a) include:

-   -   tri-n-alkylaluminums, such as trimethylaluminum,        triethylaluminum, tri-n-butylaluminum, tripropylaluminum,        tripentylaluminum, trihexylaluminum, trioctylaluminum and        tridecylaluminum;    -   branched-chain trialkylaluminums, such as triisopropylaluminum,        triisobutylaluminum, tri-sec-butylaluminum,        tri-tert-butylaluminum, tri-2-methylbutylaluminum,        tri-3-methylbutylaluminum, tri-2-methylpentylaluminum,        tri-3-methylpentylaluminum, tri-4-methylpentylaluminum,        tri-2-methylhexylaluminum, tri-3-methylhexylaluminum and        tri-2-ethylhexylaluminum;    -   tricycloalkylaluminums, such as tricyclohexylaluminum and        tricyclooctylaluminum;    -   triarylaluminums, such as triphenylaluminum and        tritolylaluminum;    -   dialkylaluminum hydrides, such as diisobutylaluminum hydride;    -   trialkenylaluminums represented by the formula        (i-C₄H₉)_(x)Al_(y)(C₅H₁₀)_(z) (wherein x, y and z are positive        numbers, and z≧2x), such as isoprenylaluminum;    -   alkylaluminum alkoxides, such as isobutylaluminum methoxide,        isobutylaluminum ethoxide and isobutylaluminum isopropoxide;    -   dialkylaluminum alkoxides, such as dimethylaluminum methoxide,        diethylaluminum ethoxide and dibutylaluminum butoxide;    -   alkylaluminum sesquialkoxides, such as ethylaluminum        sesquiethoxide and butylaluminum sesquibutoxide;    -   partially alkoxylated alkylaluminums having an average        composition represented by R^(a) _(2.5)Al(OR^(b))_(0.5;)    -   dialkylaluminum aryloxides, such as diethylaluminum phenoxide,        diethylaluminum(2,6-di-t-butyl-4-methylphenoxide),        ethylaluminumbis(2,6-di-t-butyl-4-methylphenoxide),        diisobutylalumium(2,6-di-t-butyl-4-methylphenoxide) and        isobutylaluminumbis(2,6-di-t-butyl-4-methylphenoxide);    -   dialkylaluminum halides, such as dimethylaluminum chloride,        diethylaluminum chloride, dibutylaluminum chloride,        diethylaluminum bromide and diisobutylaluminum chloride;    -   alkylaluminum sesquihalides, such as ethylaluminum        sesquichloride, butylaluminum sesquichloride and ethylaluminum        sesquibromide,    -   partially halogenated alkylaluminums, such as ethylaluminum        dichloride, propylaluminum dichloride and butylaluminum        dibromide;    -   dialkylaluminum hydrides, such as diethylaluminum hydride and        dibutylaluminum hydride;    -   partially hydrogenated alkylaluminums, e.g., alkylaluminum        dihydrides, such as ethylaluminum dihydride and propylaluminum        dihydride; and    -   partially alkoxylated and halogenated alkylaluminums, such as        ethylaluminum ethoxychloride, butylaluminum butoxychloride and        ethylaluminum ethoxybromide.

Also employable are compounds analogous to the organoaluminum compound(B-1a). For example, there can be mentioned organoaluminum compoundswherein two or more aluminum compounds are combined through a nitrogenatom, such as (C₂H₅)₂AlN(C₂H₅)Al(C₂H₅)₂.

Examples of the organoaluminum compounds (B-1b) include LiAl(C₂H₅)₄ andLiAl(C₇H₁₅)₄.

Further, other compounds such as methyllithium, ethyllithium,propyllithium, butyllithium, methylmagnesium bromide, methylmagnesiumchloride, ethylmagnesium bromide, ethylmagnesium chloride,propylmagnesium bromide, propylmagnesium chloride, butylmagnesiumbromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium,dibutylmagnesium and butylethylmagnesium are also employable as theorganometallic compounds (B-1).

Furthermore, combinations of compounds capable of producing theabove-mentioned organoaluminum compounds in the polymerization system,e.g., a combination of halogenated aluminum and alkyllithium and acombination of halogenated aluminum and alkylmagnesium, are alsoemployable.

Of the organometallic compounds (B-1) mentioned above, theorganoaluminum compounds are preferable.

The organometallic compounds (B-1) can be used singly or in combinationof two or more kinds.

(B-2) Organoaluminum Oxy-Compound

The organoaluminum oxy-compound (B-2) for use in the invention may beconventional aluminoxane or a benzene-insoluble organoaluminumoxy-compound exemplified in Japanese Patent Laid-Open Publication No.78687/1990.

The conventional aluminoxane can be prepared by, for example, thefollowing processes, and is generally obtained as a hydrocarbon solventsolution.

An organoaluminum compound such as trialkylaluminum is added to ahydrocarbon medium suspension of a compound containing adsorbed water ora salt containing water of crystallization, e.g., magnesium chloridehydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickelsulfate hydrate or cerous chloride hydrate, to allow the organoaluminumcompound to react with the adsorbed water or the water ofcrystallization.

Water, ice or water vapor is allowed to directly act on anorganoaluminum compound such as trialkylaluminum in a medium such asbenzene, toluene, ethyl ether or tetrahydrofuran.

An organotin oxide such as dimethyltin oxide or dibutyltin oxide isallowed to react with an organoaluminum compound such astrialkylaluminum in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometalliccomponent. Further, it is possible that the solvent or the unreactedorganoaluminum compound is distilled off from the recovered solution ofaluminoxane and the remainder is redissolved in a solvent or suspendedin a poor solvent for aluminoxane.

Examples of the organoaluminum compounds used for preparing thealuminoxane include the same organoaluminum compounds as described forthe organoaluminum compound (B-1a).

Of these, preferable are trialkylaluminums and tricycloalkylaluminums.Particularly preferable is trimethylaluminum.

The organoaluminum compounds can be used singly or in combination of twoor more kinds.

Examples of the solvents used for preparing the aluminoxane includearomatic hydrocarbons, such as benzene, toluene, xylene, cumene andcymene; aliphatic hydrocarbons, such as pentane, hexane, heptane,octane, decane, dodecane, hexadecane and octadecane; alicyclichydrocarbons, such as cyclopentane, cyclohexane, cyclooctane andmethylcyclopentane; petroleum fractions, such as gasoline, kerosine andgas oil; and halides of these aromatic, aliphatic and alicyclichydrocarbons, particularly chlorides and bromides thereof. Alsoemployable are ethers such as ethyl ether and tetrahydrofuran. Of thesolvents, particularly preferable are aromatic hydrocarbons andaliphatic hydrocarbons.

In the benzene-insoluble organoaluminum oxy-compound for use in theinvention, the content of Al component which is soluble in benzene at60° C. is usually not more than 10%, preferably not more than 5%,particularly preferably not more than 2%, in terms of Al atom, and thebenzene-insoluble organoaluminum oxy-compound is insoluble or sparinglysoluble in benzene.

The organoaluminum oxy-compound employable in the invention is, forexample, an organoaluminum oxy-compound containing boron and representedby the following formula (IV):

wherein R¹⁷ is a hydrocarbon group of 1 to 10 carbon atoms; and each R¹⁸may be the same or different and is a hydrogen atom, a halogen atom or ahydrocarbon group of 1 to 10 carbon atoms.

The organoaluminum compound containing boron and represented by theformula (IV) can be prepared by causing an alkylboronic acid representedby the following formula (V) to react with an organoaluminum compound inan inert solvent under an inert gas atmosphere at a temperature of −80°C. to room temperature for 1 minute to 24 hours.R¹⁷—B—(OH)₂  (V)wherein R¹⁷ is the same group as described above.

Examples of the alkylboronic acids represented by the formula (V)include methylboronic acid, ethylboronic acid, isopropylboronic acid,n-propylboronic acid, n-butylboronic acid, isobutylboronic acid,n-hexylboronic acid, cyclohexylboronic acid, phenyboronic acid,3,5-difluoroboronic acid, pentafluorophenylboronic acid and3,5-bis(trifluoromethyl)phenylboronic acid. Of these, preferable aremethylboronic acid, n-butylboronic acid, isobutylboronic acid,3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. Thealkylboronic acids are used singly or in combination of two or morekinds.

Examples of the organoaluminum compounds to be reacted with thealkylboronic acid include the same organoaluminum compounds as describedfor the organoaluminum compound (B-1a).

Of these, preferable are trialkylaluminums and tricycloalkylaluminums.Particularly preferable are trimethylaluminum, triethylaluminum andtriisobutylaluminum. The organoaluminum compounds can be used singly orin combination of two or more kinds.

The organoaluminum oxy-compounds (B-2) mentioned above are used singlyor in combination of two or more kinds.

(B-3) Compound Which Reacts With the Transition Metal Compound to FormIon Pair

The compound (B-3) which reacts with the transition metal compound toform an ion pair (referred to as “ionizing ionic compound” hereinafter),that is used in the invention, is a compound which reacts with thetransition metal compound (A) to form an ion pair, and includes Lewisacid, an ionic compound, a borane compound and a carborane compounddescribed in Japanese Patent Laid-Open Publications No. 501950/1989, No.502036/1989, No. 179005/1991, No. 179006/1991, No. 207703/1991 and No.207704/1991, and U.S. Pat. No. 5,321,106. Further, as ionizing ioniccompound, heteropoly-compound or isopoly-compound may be used.

The Lewis acid is, for example, a compound represented by BR₃ (R is aphenyl group which may have a substituent such as fluorine, methyl ortrifluoromethyl, or a fluorine atom). Examples of such compounds includetrifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris(3,5-dimethylphenyl)boron.

The ionic compound is, for example, a compound represented by thefollowing formula (VI).

In the above formula, R¹⁹ is H⁺, carbonium cation, oxonium cation,ammonium cation, phosphonium cation, cycloheptyltrienyl cation,ferrocenium cation having a transition metal, or the like.

R²⁰ to R²³ may be the same or different, and are each an organic group,preferably an aryl group or a substituted aryl group.

Examples of the carbonium cations include tri-substituted cations, suchas triphenylcarbonium cation, tri(methylphenyl)carbonium cation andtri(dimethylphenyl)carbonium cation.

Examples of the ammonium cations include trialkylammonium cations, suchas trimethylammonium cation, triethylammonium cation, tripropylammoniumcation and tributylammonium cation; N,N-dialkylanilinium cations, suchas N,N-dimethylanilinium cation, N,N-diethylanilinium cation andN,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations, suchas di(isopropyl)ammonium cation and dicyclohexylammonium cation.

Examples of the phosphonium cations include triarylphosphonium cations,such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cationand tri(dimethylphenyl)phosphonium cation.

R¹⁹ is preferably carbonium cation or ammonium cation, particularlypreferably triphenylcarbonium cation, N,N-dimethylanilinium cation orN,N-diethylanilinium cation.

Also available as the ionic compound is a trialkyl-substituted ammoniumsalt, a N,N-dialkylanilinium salt, a dialkylammonium salt and atriarylphosphonium salt.

Examples of the trialkyl-substituted ammonium salts includetriethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron,tri(n-butyl)ammoniumtetra(phenyl)boron,trimethylammoniumtetra(p-tolyl)boron,trimethylammoniumtetra(o-tolyl)boron,tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron,tripropylammoniumtetra(o,p-dimethylphenyl)boron,tri(n-butyl)ammoniumtetra(m,m-dimethylphenyl)boron,tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron,tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron andtri(n-butyl)ammoniumtetra(o-tolyl)boron.

Examples of the N,N-dialkylanilinium salts includeN,N-dimethylaniliniumtetra(phenyl)boron,N,N-diethylaniliniumtetra(phenyl)boron andN,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.

Examples of the dialkylammonium salts includedi(1-propyl)ammoniumtetra(pentafluorophenyl)boron anddicyclohexylammoniumtetra(phenyl)boron.

Further employable as the ionic compound istriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,ferroceniumtetra(pentafluorophenyl)borate,triphenylcarbeniumpentaphenylcyclopentadienyl complex,N,N-diethylaniliniumpentaphenylcyclopentadienyl complex or a boroncompound represented by the following formula (VII) or (VIII).

wherein Et is an ethyl group.

Examples of the borane compounds include:

-   -   decaborane(14);    -   salts of anions, such as bis[tri(n-butyl)ammonium]nonaborate,        bis[tri(n-butyl)ammonium]decaborate,        bis[tri(n-butyl)ammonium]undecaborate,        bis[tri(n-butyl)ammonium]dodecaborate, bis        [tri(n-butyl)ammonium]decachlorodecaborate and bis        [tri(n-butyl)ammonium]dodecachlorododecaborate; and    -   salts of metallic borane anions, such as        tri(n-butyl)ammoniumbis(dodecahydridedodecaborate)cobaltate(III)        and        bis[tri(n-butyl)ammonium]bis-(dodecahydridedodecaborate)nickelate(III).

Examples of the carborane compounds include:

-   -   salts of anions, such as 4-carbanonaborane(14),        1,3-dicarbanonaborane(13), 6,9-dicarbadecaborane(14),        dodecahydride-1-phenyl-1,3-dicarbanonaborane,        dodecahydride-1-methyl-1,3-dicarbanonaborane,        undecahydride-1,3-dimethyl-1,3-dicarbanonaborane,        7,8-dicarbaundecaborane(13), 2,7-dicarbaundecaborane(13),        undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,        dodecahydride-11-methyl-2,7-dicarbaundecaborane,        tri(n-butyl)ammonium-1-carbadecaborate,        tri(n-butyl)ammonium-1-carbaundecaborate,        tri(n-butyl)ammonium-1-carbadodecaborate,        tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,        tri(n-butyl)ammoniumbromo-1-carbadodecaborate,        tri(n-butyl)ammonium-6-carbadecaborate(14),        tri(n-butyl)ammonium-6-carbadecaborate(12),        tri(n-butyl)ammonium-7-carbaundecaborate(13),        tri(n-butyl)ammonium-7,8-dicarbaundecaborate(12),        tri(n-butyl)ammonium-2,9-dicarbaundecaborate(12),        tri(n-butyl)ammoniumdodecahydride-8-methyl-7,9-dicarbaundecaborate,        tri(n-butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,        tri(n-butyl)ammoniumundecahydride-8-butyl-7,9-dicarbaundecaborate,        tri(n-butyl)ammoniumundecahydride-8-allyl-7,9-dicarbaundecaborate,        tri(n-butyl)ammoniumundecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate        and        tri(n-butyl)ammoniumundecahydride-4,6-dibromo-7-carbaundecaborate;        and    -   salts of metallic carborane anions, such as        tri(n-butyl)ammoniumbis(nonahydride-1,3-dicarbanonaborate)cobaltate(III),        tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)ferrate(III),        tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III),        tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)nickelate(III),        tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)cuprate(III),        tri(n-butyl)ammoniumbis(undecahydride-7,8-dicarbaundecaborate)aurate(III),        tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),        tri(n-butyl)ammoniumbis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),        tri(n-butyl)ammoniumbis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III),        tris[tri(n-butyl)ammonium]bis(undecahydride-7        -carbaundecaborate)chromate(III),        bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV),        bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III)        and        bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV).

The heteropoly-compounds comprise a heteroatom such as silicon,phosphorus, titanium, germanium, arsenic or tin, and at least onepolyatom selected from vanadium, niobium molybdenum and tungsten. Forexample, phosphovanadic acid, germanovanadic acid, arsenovanadic acid,phosphoniobic acid, germanoniobic acid, siliconomolybdic acid,phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid,arsenomolybdic acid, stannnomolybdic acid, phosphotungstic acid,germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid,phosphotungstovanadic acid, germanotungstovanadic acid,phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid,phosphomolybdotungstic acid and phosphomolybdoniobic acid, salts ofthese acid with a metal of Group 1 or 2 of the periodic table such aslithium, sodium, potassium, rubidium, cesium, beryllium, magnesium,calcium, strontium or barium, and further organic salts such astriphenylethyl salts of the above acids, as well as isopoly-compounds,but not limited thereto.

The heteropoly-compounds and isopoly-compounds mentioned above may beused singly or in combination of two or more kind.

The ionizing ionic compounds (B-3) mentioned above can be used singly orin combination of two or more kinds.

If the transition metal compounds according to the invention are used ascatalyst in combination with the organoaluminum oxy-compound (B-2) suchas methylaluminoxane as a cocatalyst, olefin compounds can bepolymerized with high polymerization activities. If the ionized ioniccompound (B-3) such as triphenylcarboniumtetrakis(pentafluorophenyl)borate is used as a cocatalyst, polyolefinshaving a very high molecular weight is produced with good activities.

In the olefin polymerization catalyst of the invention, thebelow-described carrier (C) can be used if necessary, in addition to theabove-mentioned transition metal compound (A) and at least one compound(B) selected from the organometallic compound (B-1), the organoaluminumoxy-compound (B-2) and the ionized ionic compound (B-3).

(C) Carrier

The carrier (C) for use in the invention is an inorganic or organiccompound in the form of granular or particulate solid. As the inorganiccompound, porous oxide, inorganic chloride, clay, clay mineral or anion-exchange layered compound is preferable.

Examples of the porous oxides include SiO₂, Al₂O₃, MgO, ZrO, TiO₂, B₂O₃,CaO, ZnO, BaO, ThO₂; and mixtures containing these oxides, such asSiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃ andSiO₂—TiO₂—MgO. Preferable are compounds each containing at least one ofSiO₂ and Al₂O₃ as the main component.

The inorganic oxides may contain a small amount of carbonate, sulfate,nitrate or oxide component, such as Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄,Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O or Li₂O.

Though the porous oxides differ in their properties depending on thetype and the preparation process thereof, the carrier preferably used inthe invention has a particle diameter of 10 to 300 μm, preferably 20 to200 μm, a specific surface area of 50 to 1,000 m²/g, preferably 100 to700 m²/g, and a pore volume of 0.3 to 3.0 cm³/g. The carrier can be usedafter calcined at 100 to 1,000° C., preferably 150 to 700° C., ifdesired.

Examples of the inorganic chlorides employable in the invention includeMgCl₂, MgBr₂, MnCl₂ and MnBr₂. In the invention, the inorganic chloridemay be used as it is, or can be used after pulverized by a ball mill, avibration mill or the like. The inorganic chloride can be used as fineparticles of a precipitate obtained by dissolving the inorganic chloridein a solvent such as alcohol and then precipitating using precipitatingagent.

The clay for use in the invention is generally constituted mainly ofclay mineral. The ion-exchange layered-compound is a compound having acrystal structure wherein planes formed by ionic bonding or the like arelaminated in parallel to each other with a weak bond strength, and theions contained therein are exchangeable. Most of clay minerals areion-exchange layered compounds. As the clay, the clay minerals and theion-exchange layered compounds, not only natural ones but also syntheticones are employable.

Examples of such clay, clay minerals and ion-exchange layered compoundsinclude clay, clay minerals and ion crystalline compounds having layeredcrystal structures such as hexagonal closest packing type, antimonytype, CdCl₂ type and CdI₂ type.

Particular examples of the clay and the clay minerals include kaolin,bentonite, kibushi clay, gairome clay, allophane, hisingerite,pyrophyllite, mica, montmorillonite, vermiculite, chlorite,palygorskite, kaolinite, nacrite, dickite and halloysite. Particularexamples of the ion-exchange layered compounds include crystalline acidsalts of polyvalent metals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂, α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O,γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂ and γ-Ti(NH₄PO₄)₂.H₂O.

As the clay, the clay minerals and the ion-exchange layered compounds,preferable are those having a pore volume, as measured on pores having aradius of not less than 20 Å by a mercury penetration method, of notless than 0.1 cc/g, and particularly preferable are those having a porevolume of 0.3 to 5 cc/g. The pore volume is measured on the pores havinga radius of 20 to 3×10⁴ Å by a mercury penetration method using amercury porosimeter. When a compound having a pore volume, as measuredon pores having a radius of not less than 20 Å, of less than 0.1 cc/g isused, high polymerization activities are apt to be hardly obtained.

It is preferable that the clay and the clay minerals for use in theinvention are subjected to chemical treatments. A surface treatment toremove impurities attached to the surface and a treatment having aninfluence on the crystal structure of the clay are both available.Examples of such treatments include acid treatment, alkali treatment,salt treatment and organic matter treatment. The acid treatmentcontributes to not only removing impurities from the surface but alsoeluting cations such as Al, Fe and Mg present in the crystal structureto thereby increase the surface area. The alkali treatment destroys thecrystal structure of clay to bring about change in the structure of theclay. The salt treatment and the organic matter treatment can produceionic complex, molecular complex or organic derivative to change thesurface area or the distance between layers.

In the ion-exchange layered compound for use in the invention, theexchangeable ions between layers can be exchanged with other large andbulky ions utilizing ion exchange properties, whereby a layered compoundhaving enlarged distance between layers can be obtained. That is, thebulky ion plays a pillar-like roll to support the layer structure and iscalled a “pillar”. Introduction of other substances between layers of alayered material is called “intercalation”.

Examples of the guest compounds to be intercalated include cationicinorganic compounds, such as TiCl₄ and ZrCl₄; metallic alcoholates, suchas Ti(OR)₄, Zr(OR)₄, PO(OR)₃ and B(OR)₃ (R is a hydrocarbon group or thelike); and metallic hydroxide ions, such as [Al₁₃O₄(OH)₂₄]⁷⁺,[Zr₄(OH)₁₄]²⁺ and [Fe₃O(OCOCH₃)₆]⁺. These compounds can be used singlyor in combination of two or more kinds. Intercalation of these compoundscan be carried out in the presence of polymers obtained by hydrolysis ofmetallic alcoholates such as Si(OR)₄, Al(OR)₃ and Ge(OR)₄ (R is ahydrocarbon group or the like) or in the presence of colloidal inorganiccompounds such as SiO₂. Examples of the pillars include oxides producedby intercalation of the above-mentioned hydroxide ions between layersand then dehydration under heating.

The clay, clay minerals and the ion-exchange layered compounds mentionedabove may be used as they are, or may be used after subjected to atreatment of ball milling, sieving or the like. Moreover, they may beused after subjected to water adsorption or dehydration under heating.The clay, clay minerals and the ion-exchange layered compounds may beused singly or in combination of two or more kinds.

Of the above-mentioned materials, preferable are clay and clay minerals,and particularly preferable are montmorillonite, vermiculite, pectolite,teniolite and synthetic mica.

The organic compound is, for example, a granular or particulate organiccompound having a particle diameter of 10 to 300 μm. Examples of suchcompounds include (co)polymers produced using, as main components,α-olefins of 2 to 14 carbon atoms such as ethylene, propylene, 1-buteneand 4-methyl-1-pentene, (co)polymers produced using, as a maincomponent, vinylcyclohexane or styrene, and modified products thereof.

In the olefin polymerization catalyst of the invention, thebelow-described specific organic compound (D) can be used if necessary,in addition to the transition metal compound (A), at least one compound(B) selected from the organometallic compound (B-1), the organoaluminumoxy-compound (B-2) and the ionized ionic compound (B-3), and the fineparticle carrier (C).

(D) Organic Compound Component

The organic compound component which can be used if necessary functionsto improve polymerizability and properties of the resulting polymers.Examples of the organic compounds include alcohol, a phenylic compound,a carboxylic acid, a phosphorus compound and sulfonate, but the organiccompound employable in the invention is not limited thereto.

The alcohol and the phenylic compound are represented by R³¹—OH whereinR³¹ is a hydrocarbon group of 1 to 50 carbon atoms or a halogenatedhydrocarbon group of 1 to 50 carbon atoms. The alcohol is preferably ahalogen atom-containing hydrocarbon. The phenylic compound is preferablya phenylic compound wherein the α,α′-position of the hydroxyl group issubstituted with a hydrocarbon group of 1 to 20 carbon atoms.

The carboxylic acid is represented by R³²—COOH wherein R³² is ahydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbongroup of 1 to 50 carbon atoms, preferably a halogenated hydrocarbongroup of 1 to 50 carbon atoms.

Preferred examples of the phosphorus compounds include phosphoric acidshaving P—O—H bond, phosphates having P—OR bond or P═O bond, andphosphine oxide compounds.

The sulfonate is represented by the following formula (IX):

wherein M is an atom of Group 1 to Group 14 of the periodic table; R³³is a hydrocarbon group of 1 to 20 carbon atoms or a halogenatedhydrocarbon group of 1 to 20 carbon atoms; X is a hydrogen atom, ahalogen atom, a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms; m is an integerof 1 to 7; and n≦n≦7.

FIG. 1 shows steps for preparing the first olefin polymerizationcatalyst according to the invention.

In the polymerization, the components can be used in any way and in anyorder. Some examples of the processes are given below.

The component (A) and at least one component (B) selected from theorganometallic compound (B-1), the organoaluminum oxy-compound (B-2) andthe ionized ionic compound (B-3) (referred to simply as “component (B)”hereinafter) are fed to the polymerization reactor in an arbitraryorder.

A catalyst obtained by previously contacting the component (A) with thecomponent (B) is fed to the polymerization reactor.

A catalyst component obtained by previously contacting the component (A)with the component (B), and the component (B) are fed to thepolymerization reactor in an arbitrary order. In this case, thecomponents (B) may be the same or different.

A catalyst component wherein the component (A) is supported on thecarrier (C), and the component (B) are fed to the polymerization reactorin an arbitrary order.

A catalyst component wherein the component (A) and the component (B) aresupported on the carrier (C) is fed to the polymerization reactor.

A catalyst component wherein the component (A) and the component (B) aresupported on the carrier (C), and the component (B) are fed to thepolymerization reactor in an arbitrary order. In this case, thecomponents (B) may be the same or different.

A catalyst component wherein the component (B) is supported on thecarrier (C), and the component (A) are fed to the polymerization reactorin an arbitrary order.

A catalyst component wherein the component (B) is supported on thecarrier (C), the component (A) and the component (B) are fed to thepolymerization reactor in an arbitrary order. In this case, thecomponents (B) may be the same or different.

A component wherein the component (A) is supported on the carrier (C)and a component wherein the component (B) is supported on the carrier(C) are fed to the polymerization reactor in an arbitrary order.

A component wherein the component (A) is supported on the carrier (C), acomponent wherein the component (B) is supported on the component (C),and the component (B) are fed to the polymerization reactor in anarbitrary order. In this case, the components (B) may be the same ordifferent.

The component (A), the component (B) and the organic compound component(D) are fed to the polymerization reactor in an arbitrary order.

A component obtained by previously contacting the component (B) with thecomponent (D), and the component (A) are fed to the polymerizationreactor in an arbitrary order.

A component wherein the component (B) and the component (D) aresupported on the carrier (C), and the component (A) are fed to thepolymerization reactor in an arbitrary order.

A catalyst component obtained by previously contacting the component (A)with the component (B), and the component (D) are fed to thepolymerization reactor in an arbitrary order.

A catalyst component obtained by previously contacting the component (A)with the component (B), the component (B) and the component (D) are fedto the polymerization reactor in an arbitrary order.

A catalyst component obtained by previously contacting the component (A)with the component (B), and a component obtained by previouslycontacting the component (B) with the component (D) are fed to thepolymerization reactor in an arbitrary order.

A component wherein the component (A) is supported on the carrier (C),the component (B) and the component (D) are fed to the polymerizationreactor in an arbitrary order.

A component wherein the component (A) is supported on the carrier (C)and a component obtained by contacting the component (B) with thecomponent (D) are fed to the polymerization reactor in an arbitraryorder.

A catalyst component obtained by previously contacting the component(A), the component (B) and the component (D) with each other is fed tothe polymerization reactor.

A catalyst component which is obtained by previously contacting thecomponent (A), the component (B) and the component (D) with each other,and the component (B) are fed to the polymerization reactor in anarbitrary order. In this case, the components (B) may be the same ordifferent.

A catalyst component wherein the component (A), the component (B) andthe component (D) are supported on the carrier (C) is fed to thepolymerization reactor.

A catalyst component wherein the component (A), the component (B) andthe component (D) are supported on the carrier (C), and the component(B) are fed to the polymerization reactor in an arbitrary order. In thiscase, the components (B) may be the same or different.

An olefin may be prepolymerized onto the solid catalyst componentwherein the component (A) and the component (B) are supported on thecarrier (C).

In the process for olefin polymerization according to the invention, anolefin is polymerized or copolymerized in the presence of theabove-described olefin polymerization catalyst to obtain an olefinpolymer.

In the present invention, the polymerization can be carried out as anyof liquid phase polymerization, such as solution polymerization orsuspension polymerization, and gas phase polymerization.

Examples of the inert hydrocarbon media used in the liquid phasepolymerization include aliphatic hydrocarbons, such as propane, butane,pentane, hexane, heptane octane, decane, dodecane and kerosine;alicyclic hydrocarbons, such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons, such as benzene, toluene andxylene; halogenated hydrocarbons, such as ethylene chloride,chlorobenzene and dichloromethane; and mixtures of these hydrocarbons.The olefin itself can be used as the solvent.

In the polymerization of an olefin using the olefin polymerizationcatalyst, the component (A) is used in an amount of usually 10⁻¹² to10⁻² mol, preferably 10⁻¹⁰ to 10⁻³ mol, based on 1 liter of the reactionvolume. In the present invention, an olefin can be polymerized with highpolymerization activities, even if the component (A) is used in arelatively low concentration.

The component (B-1) is used in such an amount that the molar ratio ofthe component (B-1) to the transition metal atom (M) in the component(A) ((B-1)/(M)) becomes usually 0.01 to 100,000, preferably 0.05 to50,000. The component (B-2) is used in such an amount that the molarratio of the aluminum atom in the component (B-2) to the transitionmetal atom (M) in the component (A) ((B-2)/(M)) becomes usually 10 to500,000, preferably 20 to 100,000. The component (B-3) is used in suchan amount that the molar ratio of the component (B-3) to the transitionmetal atom (M) in the component (A) ((B-3)/(M)) becomes usually 1 to 10,preferably 1 to 5.

The ratio of the component (D) to the component (B) is as follows. Whenthe component (B) is the component (B-1), the component (D) is used insuch an amount that the (D)/(B-1) ratio by mol becomes 0.01 to 10,preferably 0.1 to 5. When the component (B) is the component (B-2), thecomponent (D) is used in such an amount that the molar ratio of thecomponent (D) to the aluminum atom in the component (B-2) ((D)/(B-2))becomes 0.001 to 2, preferably 0.005 to 1. When the component (B) is thecomponent (B-3), the component (D) is used in such an amount that the(D)/(B-3) ratio by mol becomes 0.01 to 10, preferably 0.1 to 5.

The temperature for the olefin polymerization using the olefinpolymerization catalyst is in the range of usually −50 to 200° C.,preferably 0 to 170° C. The polymerization pressure is in the range ofusually atmospheric pressure to 100 kg/cm², preferably atmosphericpressure to 50 kg/cm². The polymerization reaction can be carried out byany of batchwise, semi-continuous and continuous processes. Thepolymerization can be conducted in two or more stages under differentreaction conditions.

The molecular weight of the resulting polymer can be adjusted byallowing hydrogen to exist in the polymerization system or by varyingthe polymerization temperature. Further, the molecular weight can beadjusted also by using the component (B) of different type.

Examples of the olefins which can be polymerized using the olefinpolymerization catalyst include:

-   -   straight-chain or branched α-olefins of 2 to 30, preferably 3 to        20 carbon atoms, such as ethylene, propylene, 1-butene,        1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,        3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,        1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; and    -   cycloolefins of 3 to 30, preferably 3 to 20 carbon atoms, such        as cyclopentene, cycloheptene, norbornene,        5-methyl-2-norbornene, tetracyclododecene and        2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

Also employable are polar monomers. Examples of such monomers includeα,βp-unsaturated carboxylic acids, such as acrylic acid, methacrylicacid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydrideand bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid; metallic salts ofthese acids, such as sodium salts, potassium salts, lithium salts, zincsalts, magnesium salts and calcium salts; α,β-unsaturated carboxylicesters, such as methyl acrylate, ethyl acrylate, n-propyl acrylate,isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butylacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylmethacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butylmethacrylate and isobutyl methacrylate; vinyl esters, such as vinylacetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate,vinyl stearate and vinyl trifluoroacetate; and unsaturated glycidylesters, such as glycidyl acrylate, glycidyl methacrylate andmonoglycidyl itaconate. Furthermore, vinylcyclohexane, diene, polyeneand the like are also employable. The diene and the polyene are cyclicor chain compounds having 4 to 30, preferably 4 to 20 carbon atoms andhaving two or more double bonds. Examples of such compounds includebutadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene,1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene,1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene,1,7-octadiene, ethylidene norbornene, vinyl norbornene anddicyclopentadiene;

-   -   7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene,        5,9-dimethyl-1,4,8-decatriene; and further    -   aromatic vinyl compounds such as mono or poly alkylstyrenes        (e.g., styrene, o-methylstyrene, m-methylstyrene,        p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene,        m-ethylstyrene and p-ethylstyrene), functional group-containing        styrene derivatives (e.g., methoxystyrene, ethoxystyrere,        vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate,        hydroxystyrene, o-chlorostyrene, p-chlorostyrene and        divinylbenzene); and    -   3-phenylpropyrene, 4-phenylpropyrene and α-methylstyrene.

The olefin polymerization catalyst of the invention exhibits highpolymerization activities, and by the use of the catalyst, polymers ofnarrow molecular weight distribution can be obtained. When two or morekinds of olefins are used, olefin copolymers of narrow compositiondistribution can be obtained.

The olefin polymerization catalyst of the invention can be used also forthe copolymerization of an α-olefin and a conjugated diene.

Examples of the α-olefins used herein include the same straight-chain orbranched α-olefins of 2 to 30, preferably 2 to 20 carbon atoms asdescribed above. Of these, preferable are ethylene, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularlypreferable are ethylene and propylene. These x-olefins can be usedsingly or in combination or two or more kinds.

Examples of the conjugated dienes include aliphatic conjugated dienes of4 to 30, preferably 4 to 20 carbon atoms, such as 1,3-butadiene,isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene,4-methyl-1,3-pentadiene, 1,3-hexadiene and 1,3-octadiene. Theseconjugated dienes can be used singly or in combination of two or morekinds.

In the copolymerization of the α-olefin and the conjugated diene,non-conjugated diene or polyene is further employable, and examplesthereof include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene.

Second Olefin Polymerization Catalyst

The second olefin polymerization catalyst according to the invention isformed from:

-   -   (A1) a transition metal compound represented by the        below-described formula (II), and    -   (B) at least one compound selected from:        -   (B-1) an organometallic compound,        -   (B-2) an organoaluminum oxy-compound, and        -   (B-3) a compound which reacts with the transition metal            compound (A′) to form an ion pair.

First, the components for forming the olefin polymerization catalyst ofthe invention are described.

(A′) Transition Metal Compound

The transition metal compound (A′) for use in the invention is atransition metal compound represented by the following formula (II):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table,

-   -   R¹ to R¹⁰ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, an oxygen-containing group, a        nitrogen-containing group, a boron-containing group, a        sulfur-containing group, a phosphorus-containing group, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and two or more of them may be bonded to        each other to form a ring,    -   n is a number satisfying a valence of M,    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group, an        oxygen-containing group, a sulfur-containing group, a        nitrogen-containing group, a boron-containing group, an        aluminum-containing group, a phosphorus-containing group, a        halogen-containing group, a heterocyclic compound residue, a        silicon-containing group, a germanium-containing group or a        tin-containing group, and when n is 2 or greater, plural groups        X may be the same or different and may be bonded to each other        to form a ring, and    -   Y is a divalent bonding group containing at least one element        selected from the group consisting of oxygen, sulfur, carbon,        nitrogen, phosphorus, silicon, selenium, tin and boron, and when        it is a hydrocarbon group, the hydrocarbon group has 3 or more        carbon atoms.

It is preferable that at least one of R⁶ and R¹⁰, especially both ofthem, in the formula (II) is a halogen atom, a hydrocarbon group, aheterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group.

As M, R¹ to R¹⁰ and X in the formula (II), there can be used the samegroups as mentioned for M, R¹ to R⁶ and X in the formula(I),respectively. Specific examples of Y are described later on.

The transition metal compound represented by the formula (II) ispreferably a transition metal compound represented by the followingformula (II-a):

wherein M is a transition metal atom of Group 3 to Group 11, preferablyGroup 4 or 5, more preferably Group 4, of the periodic table, forexample titanium, zirconium and halfnium, especially titanium.

R¹ to R¹⁰ may be the same or different, and are each a hydrogen atom, ahalogen atom, a hydrocarbon group, a hydrocarbon-substituted silylgroup, an alkoxy group, an aryloxy group, an ester group, an amidogroup, an amino group, a sulfonamido group, a cyano group or a nitrogroup, and two or more of them may be bonded to each other to form aring,

-   -   n is a number satisfying a valence of M, usually an integer of 0        to 4, preferably 1 to 4, more preferably 1 to 3.    -   X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1        to 20 carbon atoms, an oxygen-containing group, a        sulfur-containing group or a silicon-containing group, and when        n is 2 or greater, plural groups may be the same or different        and may be bonded to each other to form a ring.    -   Y is a divalent bonding group containing at least one element        selected from the group consisting of oxygen, sulfur, carbon,        nitrogen, phosphorus, silicon, selenium, tin and boron, and when        it is a hydrocarbon group, the hydrocarbon group has 3 or more        carbon atoms.

The main chain of the bonding group Y has a structure comprisingpreferably 3 to 40, more preferably 4 to 10 atoms. The bonding group mayhave a substituent.

It is preferable that at least one of R⁶ and R¹⁰, preferably both ofthem in the formula (II-a) is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group,an ester group, an amido group, an amino group, a sulfonamido group, acyano group or a nitro group.

Specific examples of X and R¹ to R¹⁰ in the formula (II-a) are the sameas mentioned for X and R¹ to R⁶ in the formulae (I) and (I-a). X isparticularly preferably a halogen atom, a hydrocarbon group of 1 to 20carbon atoms or a sulfinato group. When n is 2 or greater, plural groupsX may be bonded to each other to form a ring such as an aromatic ring oran aliphatic ring.

Specific examples of the divalent bonding groups include chalcogenatoms, such as —O—, —S— and —Se—; nitrogen- or phosphorus-containinggroups, such as —NH—, —N(CH₃)—, —PH— and —P(CH₃)—; siliconatom-containing groups, such as —SiH₂— and —Si(CH₃)₂; tinatom-containing groups, such as —SnH₂— and —Sn(CH₃)₂; and boronatom-containing groups, such as —BH—, —B(CH₃) and —BF. Examples of thehydrocarbon groups include saturated hydrocarbon groups of 3 to 20carbon atoms, such as —(CH₂)₄—, —(CH₂)₅— and —(CH₂)₆—; cyclic saturatedhydrocarbon groups, such as cyclohexylidene and cyclohexylene; groupswherein these saturated hydrocarbon groups are partially substitutedwith 1 to 10 groups or atoms selected from hydrocarbon groups, halogenatoms (e.g., fluorine, chlorine and bromine) and hetero atoms (e.g.,oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin and boron);residual groups of cyclic hydrocarbons of 6 to 20 carbon atoms, such asbenzene, naphthalene and anthracene; residual groups of cyclic compoundscontaining hetero atoms and having 3 to 20 carbon atoms, such aspyridine, quinoline, thiophene and furan.

Examples of the transition metal compounds represented by the formula(II) are given below, but the transition metal compound are not limitedto those examples.

In the above examples, Me is methyl, Ph is phenyl.

In the present invention, transition metal compounds wherein titanium isreplaced with other metals than titanium, such as zirconium or hafnium,in the above-exemplified compounds are also employable.

In the second olefin polymerization catalyst according to the invention,the transition metal compound (A′) can be used in combination with othertransition metal compounds, as for the aforesaid transition metalcompound (A). Examples of the other transition metal compounds includethe aforesaid compounds (a-1) to (a-8).

In the second olefin polymerization catalyst according to the invention,examples of the organometallic compounds (B-1), the organoaluminumoxy-compounds (B-2) and the compounds which react with the transitionmetal compound (A′) to form an ion pair include those previouslydescribed.

In the second olefin polymerization catalyst according to the invention,the aforesaid carrier (C) can be used if necessary, in addition to theabove-mentioned transition metal compound (A′) and at least one compound(B) selected from the organometallic compound (B-1), the organoaluminumoxy-compound (B-2) and the ionized ionic compound (B-3), as in the firstolefin polymerization catalyst. Further, the aforesaid specific organiccompound (D) can also be used if necessary.

FIG. 2 shows steps for preparing the second olefin polymerizationcatalyst according to the invention.

The second olefin polymerization catalyst according to the invention canbe used for polymerizing the same olefins under the same conditions asdescribed for the first olefin polymerization catalyst.

Novel Transition Metal Compound

The novel transition metal compound according to the invention isrepresented by the following formula (III):

wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table,

-   -   m is an integer of 1 to 3,    -   R¹ is a hydrocarbon group, a hydrocarbon-substituted silyl        group, a hydrocarbon-substituted siloxy group, an alkoxy group,        an alkylthio group, an aryloxy group, an arylthio group, an        ester group, a thioester group, a sulfonester group or a        hydroxyl group,    -   R² to R⁵ may be the same or different, and are each a hydrogen        atom, a halogen atom, a hydrocarbon group, a heterocyclic        compound residue, a hydrocarbon-substituted silyl group, a        hydrocarbon-substituted siloxy group, an alkoxy group, an        alkylthio group, an aryloxy group, an arylthio group, an ester        group, a thioester group, an amido group, an imido group, an        amino group, an imino group, a sulfonester group, a sulfonamido        group, a cyano group, a nitro group, a carboxyl group, a sulfo        group, a mercapto group or a hydroxyl group,    -   R⁶ is a halogen atom, a hydrocarbon group, a        hydrocarbon-substituted silyl group, a hydrocarbon-substituted        siloxy group, an alkoxy group, an alkylthio group, an aryloxy        group, an arylthio group, an ester group, a thioester group, an        amido group, an imido group, an imino group, a sulfonester        group, a sulfonamido group or a cyano group,    -   two or more of R¹ to R⁶ may be bonded to each other to form a        ring,    -   when m is 2 or greater, two of the groups R¹ to R⁶ may be bonded        to each other, with the proviso that the groups R¹ are not        bonded to each other,    -   n is a number satisfying a valence of M, and    -   X is a halogen atom, a hydrocarbon group, an oxygen-containing        group, a sulfur-containing group, a nitrogen-containing group, a        boron-containing group, an aluminum-containing group, a        phosphorus-containing group, a halogen-containing group, a        heterocyclic compound residue, a silicon-containing group, a        germanium-containing group or a tin-containing group, and when n        is 2 or greater, plural groups X may be the same or different        and may be bonded to each other to form a ring.

As the transition metal compound of the formula (III), preferable is atransition metal compound represented by the following formula (III-a).

In the formula (III-a), M is a transition metal atom of Group 4 or Group5 of the periodic table, specifically titanium, zirconium, hafnium,vanadium, niobium or tantalum.

m is an integer of 1 to 3, preferably 2.

R¹ to R⁵ may be the same or different, and are each a hydrocarbon group,an alkoxy group or a hydrocarbon-substituted silyl group.

R⁶ is a halogen atom, a hydrocarbon group, a hydrocarbon-substitutedsilyl group, an alkoxy group, an alkylthio group or a cyano group.

Two or more of R¹ to R⁶ may be bonded to each other to form a ring.

When m is 2 or greater, two of the groups R¹ to R⁶ may be bonded to eachother, with the proviso that the groups R¹ are not bonded to each other.

n is a number satisfying a valence of M.

X is a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, halogen-containinggroup or a silicon-containing group.

Preferable X is a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing, a sulfur-containing group or a silicon containinggroup.

When n is 2 or greater, plural groups X may be the same or different andmay be bonded to each other to form a ring.

Specific examples of R¹ to R⁶ and X include those described for theabove-mentioned formula (I).

Some examples of the novel transition metal compounds are given below.

General Process for Preparing Transition Metal Compounds

The transition metal compounds of the formulae (I), (II) and (III) canbe prepared by any processes without specific limitation, for example,in the manner as described below. First, the ligand composing thetransition metal compound can be obtained by reacting a salicylaldehydecompound with a primary amine compound of the formula R¹—NH₂ (where R¹has the meanings as described above), for example an aniline compound oran alkylamine compound. In more detail, both starting compounds aredissolved in a solvent, for example those commonly used in suchreactions, preferably alcohols such as methanol and ethanol, andhydrocarbon solvents such as toluene. The resulting solution is stirredfor about 1 to 48 hours at room temperature to a reflux temperature toobtain the corresponding ligand in a good yield.

In the preparation of ligands, catalysts for example acid catalysts suchas formic acid, acetic acid and toluenesulfonic acid can be used. Inorder to proceed the reaction effectively, it is also possible to usedehydrating agents such as molecular sieves, magnesium sulfate andsodium sulfate or to perform dehydration by the Dean Stark method.

The ligand thus obtained can then be reacted with a transition metalM-containing compound, to synthesize the desired transition metalcompound. Specifically, the ligand is dissolved in a solvent, and ifnecessary, is contacted with a base to prepare a phenoxide salt,followed by mixing with a metal compound such as a metallic halide or ametallic alkylate at a low temperature and stirring for about 1 to 48hours at −78° C. to room temperature or under reflux. Any solventsusually used in such reactions may be employed and preferable are polarsolvents such as ethers, e.g., tetrahydrofuran (THF) and hydrocarbonsolvents such as toluene. Examples of the bases which may be used forpreparing the phenoxide salt include, but not limited to metallic salts,such as lithium salts (e.g., n-butyllithium) and sodium salts (e.g.,sodium hydride) and organic bases such as triethylamine and pyridine.

Depending on the properties of the compound, the step of preparing thephenoxide salt may be omitted, and the ligand can be directly reactedwith the metal compound to synthesize the corresponding transition metalcompound.

Further, it is possible that the transition metal M in the synthesizedcompound is replaced with another transition metal by conventionalmethods. Furthermore, any one of R¹ to R⁶ which is H can be substitutedby a substituent other than H at any synthesis steps.

The novel transition metal compound represented by the formula (III),preferably the formula (III-a), can be favorably used as an olefinpolymerization catalyst. If the transition metal compound is used as anolefin polymerization catalyst, (co)polymers of narrow molecular weightdistribution can be synthesized with high polymerization activities.

α-Olefin/Conjugated Diene Copolymer

The α-olefin/conjugated diene copolymer according to the inventioncomprises 1 to 99.9% by mol of constituent units derived from anα-olefin and 99 to 0.1% by mol of constituent units derived from aconjugated diene, and preferably comprises 50 to 99.9% by mol ofconstituent units derived from an α-olefin and 50 to 0.1% by mol ofconstituent units derived from a conjugated diene.

Examples of the α-olefins include the same straight-chain or branchedα-olefins of 2 to 30, preferably 2 to 20 carbon atoms as describedabove. Of these, preferable are ethylene, propylene, 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Particularlypreferable are ethylene and propylene. These α-olefins can be usedsingly or in combination or two or more kinds.

Examples of the conjugated dienes include aliphatic conjugated dienes of4 to 30, preferably 4 to 20, preferably 4 to 20 carbon atoms, such as1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene,1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene and1,3-octadiene. These conjugated dienes can be used singly or incombination of two or more kinds.

In the copolymerization of the α-olefin and the conjugated diene,non-conjugated diene or polyene is further employable, and examplesthereof include 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene.

In the polymer chain of the α-olefin/conjugated diene copolymer of theinvention, the content of 1,2-cyclopentane skeleton derived from theconjugated diene is not more than 1% by mol, preferably such a contentthat the 1,2-cyclopentadiene skeleton can be regarded to besubstantially not contained (i.e., less than 0.1% by mol). When thecontent of the 1,2-cyclopentane skeleton is less than 0.1% by mol, thecontent is regarded to be lower than the detection limit and is notintroduced into the calculation of all the conjugated diene units.

In the polymer chain of the α-olefin/conjugated diene copolymer of theinvention, the proportion of the 1,2-cyclopentane skeleton to all thediene units is not more than 20%, preferably not more than 10%. Theproportions of other insertions of the dienes (e.g., 1,4-cis, 1,4-trans,1,2-vinyl) in the α-olefin/conjugated diene copolymer are arbitrary. Theproportions can be determined by ¹³C-NMR and ¹H-NMR in accordance withthe method described in “Die Makromolekulare Chemie”, volume 192, p.2591 (1991).

The α-olefin/conjugated diene copolymer has a molecular weightdistribution (Mw/Mn) of not more than 3.5 and has a uniform compositiondistribution. The weight average molecular weight (Mw) of the copolymeris not less than 1,000, preferably not less than 5,000.

Since the α-olefin/conjugated diene copolymer has double bonds in itsmain chain or side chain, it can be variously modified. For example, byvirtue of modification with a peroxide, the double bonds can beepoxidized to introduce epoxy groups of high reactivity into thecopolymer. Such a modification makes the copolymer possible to be usedas a thermoplastic resin or a reactive resin. The double bonds can alsobe utilized in the Diels-Alder reaction or the Michael additionreaction. Further, in case of the copolymer having double bonds in themain chain, the copolymer can be improved in heat resistance and ozoneresistance by selectively hydrogenating the double bonds to saturatethem.

The α-olefin/conjugated diene copolymer of the invention may be modifiedpartially or fully with an unsaturated carboxylic acid, its derivativeor an aromatic vinyl compound, and the degree of modification ispreferably in the range of 0.01 to 30% by weight.

The monomer used for the modification (referred to as “graft monomer”hereinafter) is, for example, an unsaturated carboxylic acid, itsderivative or an aromatic vinyl compound. Examples of the unsaturatedcarboxylic acids include acrylic acid, methacrylic acid, maleic acid,fumaric acid and itaconic acid. Examples of the derivatives ofunsaturated carboxylic acids include acid anhydrides, esters, amides,imides and metallic salts thereof, such as maleic anhydride, citraconicanhydride, itaconic anhydride, methyl acrylate, methyl methacrylate,ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethylmaleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate,diethyl itaconate, acrylamide, methacrylamide, maleic acid monoamide,maleic acid diamide, maleic acid-N-monoethylamide, maleicacid-N,N-diethylamide, maleic acid-N-monobutylamide, maleicacid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide,fumaric acid-N-monoethylamide, fumaric acid-N,N-diethylamide, fumaricacid-N-monobutylamide, fumaric acid-N,N-dibutylamide, maleimide,N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodiummethacrylate, potassium acrylate and potassium methacrylate. Of thegraft monomers, maleic anhydride is preferably employed.

Examples of the aromatic vinyl compounds include:

-   -   styrene;    -   mono or polyalkylstyrenes, such as o-methylstyrene,        m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene,        o-ethylstyrene, m-ethylstyrene and p-ethylstyrene;    -   functional group-containing styrene derivatives, such as        methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl        vinylbenzoate, vinylbenzyl acetate, hydroxystyrene,        o-chlorostyrene, p-chlorostyrene and divinylbenzene; and    -   others, such as 3-phenylpropylene, 4-phenylbutene and        a-methylstyrene. Of these, styrene or 4-methoxystyrene is        preferable.

For graft copolymerizing the α-olefin/conjugated diene copolymer withthe graft monomer to prepare a modified copolymer, various knownprocesses are available.

For example, the α-olefin/conjugated diene copolymer and the graftmonomer are heated at a high temperature in the presence or absence of asolvent and in the presence or absence of a radical initiator to performgraft copolymerization. In the reaction, the graft monomers may be usedin combination.

In order to prepare a partially or wholly graft-modifiedα-olefin/conjugated diene copolymer having a graft ratio of 0.01 to 30%by weight, it is preferable from the viewpoint of industrial productionthat a graft-modified α-olefin/conjugated diene copolymer having a highgraft ratio is prepared and the thus graft-modified copolymer is thenmixed with an unmodified α-olefin/conjugated diene copolymer to adjustthe graft ratio, because the concentration of the graft monomer in thecomposition can be adjusted as desired. It is also possible that a givenamount of a graft monomer is blended with the α-olefin/conjugated dienecopolymer from the first to perform graft modification. Referring to thedegree of modification of the α-olefin/conjugated diene copolymer withthe graft monomer, the graft ratio to the whole resin composition is inthe range of preferably 0.01 to 30% by weight, particularly preferably0.05 to 10% by weight.

The α-olefin/conjugated diene copolymer of the invention (including theabove-mentioned modified product) may be blended with (i) a polyolefinresin and optionally, with (ii) a filler to form resin compositionsuseful for various applications.

(i) Polyolefin Resin

The polyolefin resin (i) which may be blended with theα-olefin/conjugated diene copolymer of the invention may be any of acrystalline polyolefin and an amorphous polyolefin, or may be a mixtureof thse polyolefin resins.

The crystalline polyolefin is, for example, a homopolymer or a copolymerof an α-olefin of 2 to 20 carbon atoms or a cycloolefin. The amorphouspolyolefin is, for example, a copolymer of one or more α-olefins of 2 to20 carbon atoms and one or more cycloolefins.

Examples of the α-olefins of 2 to 20 carbon atoms include ethylene,propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,4,4-dimethyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene,3-ethyl-1-hexene, 4-ethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-octene,3-methyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Examples of the cycloolefins include cyclopentene, cycloheptene,cyclohexene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene and2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

Examples of the crystalline polyolefin resins include the following(co)polymers (1) to (11). Of the copolymers, particularly preferable arethe copolymers (3) and (5).

-   -   (1) Ethylene homopolymer (produced by any of low-pressure and        high-pressure processes)    -   (2) Copolymer of ethylene and not more than 20% by mol of        another α-olefin, vinyl monomer (e.g., vinyl acetate, ethyl        acrylate) or cycloolefin    -   (3) Propylene homopolymer    -   (4) Random copolymer of propylene and not more than 20% by mol        of another α-olefin    -   (5) Block copolymer of propylene and not more than 30% by mol of        another α-olefin    -   (6) 1-Butene homopolymer    -   (7) Random copolymer of 1-butene and not more than 20% by mol of        another α-olefin    -   (8) 4-Methyl-1-pentene homopolymer    -   (9) Random copolymer of 4-methyl-1-pentene and not more than 20%        by mol of another α-olefin    -   (10) Cyclopentene homopolymer    -   (11) Random copolymer of cyclopentene and not more than 20% by        mol of another α-olefin

As the “another α-olefin” in the above (co)polymers (1) to (11),ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octenefrom among the aforesaid examples is preferably employed. As thecycloolefin, cyclopentene, cyclohexene, norbornene or tetracyclododeceneis preferably employed.

The crystalline polyolefin resin desirably has a melt flow rate(measured at 230° C. under a load of 2.16 kg in accordance with ASTMD1238-65T) of 0.01 to 100 g/10 min, preferably 0.3 to 70 g/10 min, and acrystallinity, as measured by X-ray diffractometry, of usually 5 to100%, preferably 20 to 80%.

The crystalline polyolefin resin can be prepared by a conventionalprocess.

Examples of the amorphous polyolefin resins include the following(co)polymers.

-   -   (1) Norbornene homopolymer    -   (2) Copolymer of ethylene and norbornene, or copolymer of        ethylene, norbornene and another α-olefin    -   (3) Copolymer of ethylene and tetracyclododecene, or copolymer        of ethylene, tetracyclododecene and another α-olefin        (ii) Filler

As the fillers (ii), which may be blended with the α-olefin/conjugateddiene copolymer of the invention, those generally used can be usedwithout specific limitation.

Examples of the inorganic fillers include:

-   -   powdered fillers, such as silicates (e.g., powdered talc,        kaolinite, calcined clay, pyrophillite, sericite, wollastonite),        carbonates (precipitated calcium carbonate, heavy calcium        carbonate, magnesium carbonate), hydroxides (e.g., aluminum        hydroxide, magnesium hydroxide), oxides (e.g., zinc oxide, zinc        white, magnesium oxide), and synthetic silicic acids or        silicates (e.g., hydrated calcium silicate, hydrated aluminum        silicate, hydrated silicic acid, silicic anhydride);    -   flaky fillers, such as mica;    -   fibrous fillers, such as basic magnesium sulfate whisker,        calcium titanate whisker, aluminum borate whisker, sepiolite,        PMF (processed mineral fiber), xonotlite, potassium titanate and        ellestadite; and    -   balloon fillers, such as glass balloon and fly ash balloon.

These fillers can be used singly or in combination of two or more kinds.

When the α-olefin/conjugated diene copolymer is blended with thepolyolefin resin (i) and the filler (ii), the α-olefin/conjugated dienecopolymer is desirably contained in an amount of 10 to 90 parts byweight, preferably 15 to 80 parts by weight, more preferably 20 to 75parts by weight, based on 100 parts by weight of the total of theα-olefin/conjugated diene copolymer, the polyolefin resin (i) and thefiller (ii). If the content of the α-olefin/conjugated diene copolymeris used in this amount, the α-olefin/conjugated diene copolymercomposition has excellent moldability and is capable of providing moldedproducts having not only excellent impact resistance, weatheringresistance and heat stability but also excellent rigidity, strength andheat resistance.

The polyolefin resin (i) is contained in an amount of 1 to 99 parts byweight, preferably 10 to 85 parts by weight, more preferably 10 to 85parts by weight, based on 100 parts by weight of the total of theresulting composition.

If the polyolefin resin (i) is used in this amount, the compositionhaving not only excellent impact resistance and cold resistance but alsoexcellent rigidity, strength, heat resistance and moldability can beobtained.

The filler (ii) is contained in an amount of 0 to 40 parts by weight,preferably 0 to 30 parts by weight, based on 100 parts by weight of thetotal of the resulting composition. If the filler (ii) is contained inthis amount, the composition having excellent rigidity, surfaceappearance and heat resistance can be obtained.

Further, to the α-olefin/conjugated diene copolymer composition, variousadditives, such as nucleating agents, antioxidants, hydrochloric acidabsorbers, heat stabilizers, light stabilizers, ultraviolet lightabsorbers, lubricants, antistatic agensts, flame retardants, pigments,dyes, dispersants, copper harm inhibitors, neutralizing agents, foamingagents, plasticizers, anti-foaming agents, crosslinking agents,crosslinking aids, crosslinking accelerators, flow property improvers(e.g., peroxide), weld strength improvers, processing aids, weatheringstabilizers and blooming inhibitors, may be added in an amount notdetrimental to the objects of the invention. These optional additivesmay be used in combination of two or more kinds.

EFFECT OF THE INVENTION

The olefin polymerization catalyst according to the invention exhibitshigh polymerization activities on olefins.

In the process for olefin polymerization according to the invention, anolefin (co)polymer of narrow molecular distribution can be produced withhigh polymerization activities. When an α-olefin and a conjugated dieneare copolymerized, a copolymer containing almost no 1,2-cyclopentaneskeleton in the polymer chain can be produced.

The novel transition metal compound according to the invention is usefulfor an olefin polymerization catalyst, and provides an olefin(co)polymer of narrow molecular weight distribution with highpolymerization activities.

The α-olefin/conjugated diene copolymer according to the invention has anarrow molecular weight distribution and contains almost no cyclopentaneskeleton in the polymer chain.

EXAMPLE

The present invention is further described with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

Structures of the compounds obtained by Synthesis Examples weredetermined by 270 MHz ¹H-NMR (GSH-270 of Japan Electron OpticsLaboratory Co., Ltd.), FT-IR (SHIMAZU FTIR-82OOD), FD-mass spectrometry(SX-102A of Japan Electron Optics Laboratory Co., Ltd.), metal contentanalysis (SHIMAZU ICPS-8000, ICP method after dry ashing and dilutenitric acid dissolution), and carbon, hydrogen and nitrogen contentanalysis (CHNO type of Helaus Co.).

Structures of the compounds A-1 and B-1 were further decided by X-raycrystal structure analysis. The measurement was made by effecting Mo—Ka-ray irradiation using a Rigaku AFC7R four-axis diffractometer. Thestructure analysis was made by a direct method (SIR92), and thestructure optimization was made in accordance with TeXan crystalstructure analysis program.

Further, the intrinsic viscosity [η] was measured indecahydronaphthalene at 135° C. The molecular weight distribution(Mw/Mn) was measured by the gas permeation chromatography (GPC) usingo-dichlorobenzene as a solvent at 140° C.

Specific syntheses of ligands are given below.

Ligand Synthesis Example 1

Synthesis of Ligand (L1)

To a 100 ml reactor thoroughly purged with nitrogen, 40 ml of ethanol,0.71 g (7.62 mmol) of aniline and 1.35 g (7.58 mmol) of3-t-butylsalicylaldehyde were introduced, and they were stirred at roomtemperature for 24 hours. The reaction solution was concentrated underreduced pressure to remove the solvent. Then, 40 ml of ethanol was addedagain, and the mixture was stirred at room temperature for 12 hours. Thereaction solution was concentrated under reduced pressure to obtain 1.83g (7.23 mmol, yield: 95%) of a compound represented by the followingformula (L1) as an orange oil.

¹H-NMR (CDCl₃): 1.47 (s, 9H), 6.88 (dd, 1H), 7.24-7.31 (m, 4H),7.38-7.46 (m, 3H), 8.64 (s, 1H), 13.95 (s, 1H)

IR (neat): 1575, 1590, 1610 cm⁻¹

FD-mass spectrometry: 253

Ligand Synthesis Example 2

Synthesis of Ligand (L2)

To a 100 ml reactor thoroughly purged with nitrogen, 30 ml of ethanol,1.34 g (9.99 mmol) of a-naphthylamine and 1.40 g (7.86 mmol) of3-t-butylsalicylaldehyde were introduced. After addition of 5 g ofmolecular sieves 3A, the mixture was stirred under reflux for 8 hoursand then at room temperature for 12 hours. The reaction solution wasconcentrated under reduced pressure and the residue was purified using asilica gel column to obtain 2.35 g (7.75 mmol, 98% yield) of a compoundas an orange oil represented by the following formula (L2).

¹H-NMR (CDCl₃): 1.50 (s, 9H), 6.90-7.90 (m, 11H), 8.30-8.50 (m, 1H),13.90 (s, 1H)

FD-mass spectrometry: 303

Ligand Synthesis Example 3

Synthesis of Ligand (L3)

To a 100 ml reactor thoroughly purged with nitrogen, 30 ml of ethanol,0.90 g (12.0 mmol) of t-butylamine and 1.78 g (10.0 mmol) of3-t-butylsalicylaldehyde were introduced. After addition of 5 g ofmolecular sieves 3A, the mixture was stirred at room temperature for 12hours. The reaction solution was concentrated under reduced pressure andthe residue was purified using a silica gel column to obtain 2.17 g (9.3mmol, 93% yield) of a compound as an fluorescent yellow oil representedby the following formula (L3).

¹H-NMR (CDCl₃): 1.20 (s, 9H), 1.42 (s, 9H), 6.50-7.50 (m, 3H), 8.38 (s,1H), 13.80 (s, 1H)

FD-mass spectrometry: 233

Ligand Synthesis Examples 4-42

Ligands L4 to L42 were synthesized in the similar manner as in theforgoing Ligand Synthesis Examples.

The identification of their structures were made by ¹H-NMR and FD-massspectrometry.

Specific syntheses of transition metal compounds according to thepresent invention are given below.

Synthesis of Compound A-1

To a 300 ml reactor thoroughly dried and purged with argon, 1.785 g(7.05 mmol) of compound L1 and 100 ml of diethyl ether were introduced,and they were cooled to −78° C. and stirred. After 4.78 ml ofn-butyllithium (1.55 mmol/ml n-hexane solution, 7.40 mmol) was dropwiseadded over a period of 5 minutes, the temperature was slowly raised toroom temperature, and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was slowlydropwise added to a mixture of 7.05 ml of a titanium tetrachloridesolution (0.5 mmol/ml heptane solution, 3.53 mmol) and 40 ml of diethylether which had been been cooled to −78° C.

After the dropwise addition was completed, the temperature was slowlyraised to room temperature with stirring. After stirring for another 8hours at room temperature, the reaction solution was filtered with aglass filter, and the resulting solid was dissolved and washed with 50ml of methylene chloride to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 10 ml of methylene chloride. To the solution was thenslowly added 70 ml of pentane with stirring. The mixture was allowed tostand at room temperature to precipitate red brown crystals. Thecrystals were separated by filtration with a glass filter, washed withpentane and then vacuum dried to obtain 1.34 g (2.15 mmol, yield: 61%)of compound A-1 represented by the following formula as red browncrystals.

¹H-NMR (CDCl₃): 1.35 (s, 18H), 6.82-7.43 (m, 16H), 8.07 (s, 2H)

IR (KBr): 1550, 1590, 1600 cm⁻¹

FD-mass spectrometry: 622 (M+)

Elemental analysis:

-   -   Ti: 7.7% (7.7)    -   C: 65.8% (65.5), H: 6.0% (5.8), N: 4.5% (4.5)

Calculated values in pharentheses.

Melting point: 265° C.

X-ray crystal structure analysis: The structure of compound A-1 is shownin FIG. 3.

Synthesis Example 2

Synthesis of Compound B-1

To a 200 ml reactor thoroughly dried and purged with argon, 1.53 g (6.04mmol) of compound L1 and 60 ml of tetrahydrofuran were introduced, andthey were cooled to −78° C. and stirred. After 4.1 ml of n-butyllithium(1.55 mmol/ml n-hexane solution, 6.34 mmol) was dropwise added over aperiod of 5 minutes, the temperature was slowly raised to roomtemperature, and stirring was continued at room temperature for 4 hours.To the reaction solution was added 10 ml of tetrahydrofuran, and themixture was slowly added to a solution of 0.70 g of zirconiumtetrachloride (purity: 99.9%, 3.02 mmol) in 30 ml of tetrahydrofuranwhich had been cooled to −78° C. After the addition, the temperature wasslowly raised to room temperature. The reaction solution was stirred for2 hours at room temperature and then further stirred for another 4 hoursunder reflux.

The reaction solution was concentrated under reduced pressure, and thesolid precipitated was washed with 50 ml of methylene chloride andfiltered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 30 ml of diethyl ether. The solution was allowed to standfor one day at −20° C. in a nitrogen atmosphere to precipitate yellowcrystals. The solid was separated by filtration, washed with hexane andthen vacuum dried to obtain 1.09 g (1.63 mmol, yield: 54%) of compoundB-1 represented by the following formula as fluorescent yellow crystals.

¹H-NMR (CDCl₃): 1.33 (s, 18H), 6.78-7.42 (m, 16H), 8.12 (s, 2H)

IR (KBr): 1550, 1590, 1605 cm⁻¹

FD-mass spectrometry: 664 (M+)

Elemental analysis:

-   -   Zr: 13.5% (13.7)    -   C: 61.0% (61.2), H: 5.5% (5.4), N: 4.2% (4.2)

Calculated values in pharentheses.

Melting point: 287° C.

X-ray crystal structure analysis: The structure of compound B-1 is shownin FIG. 4.

Synthesis Example 3

Synthesis of Compound C-1

To a 100 ml reactor thoroughly dried and purged with argon, 0.66 g (2.60mmol) of compound (L1) and 8 ml of diethyl ether were introduced, andthey were cooled to −78° C. and stirred. After 1.81 ml of n-butyllithium(1.55 mmol/ml n-hexane solution, 2.80 mmol) was dropwise added over aperiod of 5 minutes, the temperature was slowly raised to roomtemperature, and stirring was continued at room temperature for 2 hours.To the reaction solution was added 10 ml of tetrahydrofuran, and themixture was slowly added to a solution of 0.385 g of hafniumtetrachloride (purity: 99.9%, 3.02 mmol) in 10 ml of tetrahydrofuranwhich had been cooled to −78° C. After the addition, the temperature wasslowly raised to room temperature. The reaction solution was stirred for2 hours at room temperature and then further stirred for another 2 hoursunder heating at 50° C.

The reaction solution was concentrated under reduced pressure, and thesolid precipitated was washed with 20 ml of methylene chloride andfiltered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasreslurried in 10 ml of diethyl ether at room temperature for 1 hour andseparated by filtration. The solid was washed with hexane and thenvacuum dried to obtain 0.33 g (0.40 mmol, yield: 33%) of compound C-1represented by the following formula as fluorescent yellow whitecrystals.

¹H-NMR (CDCl₃): 1.30 (s, 18H), 6.70-7.50 (m, 16H), 8.18 (s, 2H)

FD-mass spectrometry: 754 (M+)

Elemental analysis:

-   -   Hf: 23.5% (23.7)    -   C: 54.4% (54.2), H: 4.8% (4.8), N: 3.6% (3.7)

Calculated values in pharentheses.

Melting point: 277° C.

Synthesis Example 4

Synthesis of Compound D-1

To a 100 ml reactor thoroughly dried and purged with argon, 0.61 g (2.40mmol) of compound (L1) and 10 ml of diethyl ether were introduced, andthey were cooled to −78° C. and stirred. After 1.61 ml of n-butyllithium(1.55 mmol/ml n-hexane solution, 2.50 mmol) was dropwise added over aperiod of 5 minutes, the temperature was slowly raised to roomtemperature, and stirring was continued at room temperature for 4 hours.The reaction solution was slowly added to a solution of 0.385 g ofhafnium tetrachloride (purity: 99.9%, 3.02 mmol) in 10 ml of diethylether which had been cooled to −78° C. After the addition, thetemperature was slowly raised to room temperature, and the reactionsolution was stirred for 4 hours at room temperature.

The reaction solution was concentrated under reduced pressure, and thesolid precipitated was washed with 20 ml of methylene chloride andfiltered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 1 ml of diethyl ether. To the solution was slowly added 10ml of hexane with stirring to precipitate black green solid. The solidwas separated by filtration, reslurried and washed with hexane at roomtemperature for 1 hour and then vacuum dried to obtain 0.55 g (0.88mmol, yield: 73%) of compound D-1 represented by the following formulaas a blue black powder.

¹H-NMR (CDCl₃): unmeasurable because of paramagnetic metal complex.

FD-mass spectrometry: 625 (M+)

Elemental analysis:

-   -   V: 8.4% (8.1)    -   C: 65.3% (65.2), H: 5.5% (5.8), N: 4.5% (4.8)

Calculated values in pharentheses.

Synthesis Example 5

Synthesis of Compound E-1

To a 100 ml reactor thoroughly dried and purged with argon, 0.61 g (2.40mmol) of compound (L1) and 10 ml of diethyl ether were introduced, andthey were cooled to −78° C. and stirred. After 1.60 ml of n-butyllithium(1.55 mmol/ml n-hexane solution, 2.50 mmol) was dropwise added over aperiod of 5 minutes, the temperature was slowly raised to roomtemperature, and stirring was continued at room temperature for 4 hours.To the reaction solution was added 5 ml of tetrahydrofuran, and themixture was slowly added to a solution of 0.34 g of niobiumpentachloride (purity: 95%, 1.20 mmol) in 10 ml of tetrahydrofuran whichhad been cooled to −78° C. After the addition, the temperature wasslowly raised to room temperature, and the reaction solution was stirredat room temperature for 15 hours.

The reaction solution was concentrated under reduced pressure, and thesolid precipitated was washed with 20 ml of methylene chloride andfiltered with a glass filter to remove insolubles. The filtrate wasconcentrated under reduced pressure, and the solid precipitated wasdissolved in 3 ml of diethyl ether. To the solution was slowly dropwiseadded 12 ml of hexane at room temperature with stirring to precipitateblack solid. The solid was separated by filtration, reslurried andwashed with hexane at room temperature for 1 hour and then vacuum driedto obtain 0.36 g (0.51 mmol, yield: 43%) of fluorescent yellow whitecompound E-1 represented by the following formula.

¹H-NMR (CDCl₃): 1.46 (s, 18H), 7.20-7.50 (m, 16H), 8.65 (s, 2H)

FD-mass spectrometry: 702 (M+)

Elemental analysis:

-   -   Nb: 13.0% (13.2)    -   C: 58.4% (58.0), H: 5.0% (5.2), N: 3.9% (4.0)

Calculated values in pharenthesis

Synthesis Example 6

Synthesis of Compound F-1

To a 100 ml reactor thoroughly dried and purged with argon, 0.61 g (2.40mmol) of compound (L1) and 10 ml of toluene were introduced, and theywere cooled to −40° C. and stirred. To the mixture, 0.43 g of solidtantalum pentachloride (purity: 99.99%, 1.20 mmol) was slowly added.After the addition, the temperature was slowly raised to roomtemperature, then further raised to 60° C., and stirring was continuedfor 16 hours.

To the reaction solution was added 30 ml of methylene chloride, and theinsolubles were filtered. The filtrate was concentrated under reducedpressure, and to the concentrate was added 8 ml of hexane to separateout an orange viscous oil. The oil portion was separated and dissolvedin 1 ml of diethyl ether. To the solution was slowly dropwise added 9 mlof hexane with stirring to precipitate bright yellow solid. The solidwas separated by filtration, reslurried and washed hexane at roomtemperature for 1 hour and then vacuum dried to obtain 0.15 g (0.26mmol, yield: 22%) of compound F-1 represented by the following formulaas a bright yellow powder.

¹H-NMR (CDCl₃): 1.50 (s, 9H), 6.80-7.75 (m, 8H), 8.23 (s, 1H)

FD-mass spectrometry: 575 (M+)

Elemental analysis:

-   -   Ta: 31.0% (31.5)    -   C: 58.4% (58.0), H: 3.3% (3.2), N: 4.5% (4.8)

Calculated values in pharentheses.

Synthesis Example 7

Synthesis of Compound A-2

After charging 0.91 g (3.0 mmol) of compound L2 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.90 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.3 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was cooledto −78° C. and then slowly added dropwise to a mixture of 3.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.50mmol) and 10 ml of diethyl ether. After completion of the dropwiseaddition, stirring was continued while slowly increasing the temperatureto room temperature. After further stirring for 8 hours at roomtemperature, the reaction solution was filtered with a glass filter. Theresulting solid was dissolved and washed in 50 ml of methylene chloride,and the insoluble portion was removed by filtration. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with diethyl ether and hexane and dried under reducedpressure to obtain 0.53 g (0.73 mmol, 49% yield) of compound A-2 as darkbrown crystals represented by the formula given below.

¹H-NMR(CDCl₃): 0.86 (s,18H), 6.85-7.05 (m,6H), 7.15-7.30 (m,4H),7.35-7.90 (m,10H), 8.45 (s,2H)

FD-mass spectrometry: 722 (M+)

Elemental analysis: Ti: 6.6% (6.6)

C: 69.9% (69.7), H: 5.5% (5.6), N: 3.4% (3.9)

Calculated values in parentheses.

Synthesis Example 8

Synthesis of Compound B-2

After charging 0.91 g (3.0 mmol) of compound L2 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.94 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.0 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was thenslowly added dropwise to a 10 ml tetrahydrofuran solution containingzirconium tetrachloride (0.35 g, 1.50 mmol) which had been cooled to−78° C. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 8 hours at room temperature, the reactionsolution was concentrated to dryness, the residue was dissolved andwashed in 50 ml of methylene chloride, and then the insoluble portionwas removed by filtration. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.21 g (0.73 mmol,18% yield) of compound B-2 as yellow crystals represented by the formulagiven below.

¹H-NMR(CDCl₃): 1.11-1.70 (m,18H), 6,80-8.30 (m,20H), 8.33-8.48 (m,2H)

FD-mass spectrometry: 766 (M+)

Elemental analysis: Zr: 12.1% (11.9)

Calculated value in parentheses.

Synthesis Example 9

Synthesis of Compound A-3

After charging 0.70 g (3.0 mmol) of compound L3 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.90 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.3 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was cooledto −78° C. and then 3.0 ml of a titanium tetrachloride solution (0.5mmol/ml heptane solution, 1.50 mmol) was slowly added dropwise. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filteredwith a glass filter. The resulting solid was dissolved and washed in 50ml of methylene chloride, and the insoluble portion was removed byfiltration. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.15 g (0.26 mmol, 17% yield) ofcompound A-3 as yellow brown crystals represented by the formula givenbelow.

¹H-NMR(CDCl₃): 1.20 (s,18H), 1.41 (s,18H), 6.85-7.05 (m,2H), 7.20-7.80(m, 4H), 8.58 (s, 2H)

FD-mass spectrometry: 582 (M+)

Elemental analysis: Ti: 8.2% (8.2)

C: 62.1% (61.8), H: 7.1% (7.6), N: 4.7% (4.8)

Calculated values in parentheses.

Synthesis Example 10

Synthesis of Compound B-3

After charging 0.70 g (3.0 mmol) of compound L3 and 30 ml oftetrahydrofuran into a 100 ml reactor which had been adequately driedand substituted with argon, they were cooled to −78° C. and stirred.After dropwise adding 1.90 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.3 mmol) over 5 minutes, the temperature was slowly increasedto room temperature and stirring was continued for 4 hours at roomtemperature to prepare a lithium salt solution. The solution was cooledto −78° C. and solid zirconium tetrachloride (0.38 g, 1.65 mmol) wasadded. After completion of the addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the solvent was distilled offfrom the reaction solution, the resulting solid was dissolved and washedin 50 ml of methylene chloride, and the insoluble portion was removed byfiltration. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with methylene chloride andhexane and dried under reduced pressure to obtain 0.31 g (0.50 mmol, 30%yield) of compound B-3 as a yellow powder represented by the formulagiven below.

¹H-NMR(CDCl₃): 1.34 (s,18H), 1.44 (s,18H), 6.79 (dd,2H), 7.11 (d,2H),7.27 (d,2H), 8.34 (s,2H)

FD-mass spectrometry: 626 (M+)

Elemental analysis: Zr: 15.0% (14.6)

C: 52.9 (57.5), H: 7.2 (7.1), N: 4.7 (4.8)

Calculated values in parentheses.

Synthesis Example 11

Synthesis of Compound A-4

After charging 0.50 g (2.02 mmol) of compound L4 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.36 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 2.09 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 2.00 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.00 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, the reaction solution wasfiltered with a glass filter. The resulting solid was dissolved andwashed in 50 ml of methylene chloride, and the insoluble portion wasremoved by filtration. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with methylenechloride and hexane and dried under reduced pressure to obtain 0.34 g(0.56 mmol, 56% yield) of compound A-4 as a dark brown powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 7.00-7.90 (m,22H), 8.35-8.55 (m,2H)

FD-mass spectrometry: 610 (M+)

Elemental analysis: Ti: 7.8% (7.8)

C: 62.4% (66.8), H: 4.9% (4.4), N: 4.2% (4.6)

Calculated values in parentheses.

Synthesis Example 12

Synthesis of Compound B-4

After charging 0.46 g (1.86 mmol) of compound L4 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.30 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 2.00 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then solid zirconium tetrachloride (0.21 g, 0.91mmol) was added. After completion of the addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 16 hours at room temperature, 20 ml ofdiethyl ether was added and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.25 g (0.38 mmol, 42% yield) ofcompound B-4 as a yellow-brownish green powder represented by theformula given below.

¹H-NMR(CDCl₃): 6.90-7.95 (m,22H), 8.40-8.60 (m,2H)

FD-mass spectrometry: 652 (M+)

Elemental analysis: Zr: 14.3% (13.9)

Calculated value in parentheses.

Synthesis Example 13

Synthesis of Compound A-5

After charging 0.83 g (3.00 mmol) of compound L5 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.00 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.08 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 3.00 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.50 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withmethylene chloride and hexane and dried under reduced pressure to obtain0.07 g (0.10 mmol, 7% yield) of compound A-5 as an ocher powderrepresented by the formula given below.

FD-mass spectrometry: 666 (M+)

Elemental analysis: Ti: 7.3% (7.2)

Calculated value in parentheses.

Synthesis Example 14

Synthesis of Compound B-5

After charging 0.50 g (1.82 mmol) of compound L5 and 15 ml oftetrahydrofuran into a 100 ml reactor which had been adequately driedand substituted with argon, they were cooled to −78° C. and stirred.After dropwise adding 1.36 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 2.09 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C. and then a 10 ml tetrahydrofuran solution containing azirconium tetrachloride.2THF complex (0.38 g, 1.00 mmol) was addeddropwise. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 10 hours at room temperature and 4 hours at50° C., the insoluble portion was removed with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with methylene chloride, diethyl ether andhexane and dried under reduced pressure to obtain 0.04 g (0.05 mmol, 5%yield) of compound B-5 as a yellow-brownish green powder represented bythe formula given below.

FD-mass spectrometry: 710 (M+)

Elemental analysis: Zr: 13.3% (12.8)

Calculated value in parentheses.

Synthesis Example 15

Synthesis of Compound A-6

After charging 0.93 g (3.01 mmol) of compound L6 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.1 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.23 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C. and then 3.0 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.50 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was recrystallized with hexaneat −78° C. and dried under reduced pressure to obtain 0.41 g (0.56 mmol,37% yield) of compound A-6 as a brown powder represented by the formulagiven below.

¹H-NMR(CDCl₃): 1.21 (s,18H), 1.30 (s,18H), 6.70-7.70 (m,14H), 8.08(s,2H)

FD-mass spectrometry: 734 (M+)

Elemental analysis: Ti: 6.6% (6.5)

C: 67.9% (68.6), H: 7.4% (7.1), N: 3.9% (3.8)

Calculated values in parentheses.

Synthesis Example 16

Synthesis of Compound B-6

After charging 0.93 g (3.01 mmol) of compound L6 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.1 ml of n-butyllithium (1.54 mmol/ml n-hexanesolution, 3.23 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C. and then solid zirconium tetrachloride (0.35 g, 1.50mmol) was added. After completion of the addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 14 hours at room temperature, 20 ml ofmethylene chloride was added, and the insoluble portion was removed witha glass filter. The filtrate was concentrated under reduced pressure,and the deposited solid was recrystallized with hexane at −78° C. anddried under reduced pressure to obtain 0.55 g (0.71 mmol, 47% yield) ofcompound B-6 as a brownish green powder represented by the formula givenbelow.

¹H-NMR(CDCl₃): 1.20-1.80 (m,36H), 6.70-7.70 (m,14H), 7.80-7.90 (m,2H)

FD-mass spectrometry: 776 (M+)

Elemental analysis: Zr: 11.2% (11.7)

Calculated value in parentheses.

Synthesis Example 17

Synthesis of Compound A-7

After charging 1.0 g (3.66 mmol) of compound L7 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.48 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.84 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixture of 3.66 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.83 mmol) and 20ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the reaction solution was filtered with a glassfilter. The filtrate was concentrated under reduced pressure, and thedeposited solid was reslurried with hexane. The slurry was filtered toremove the solvent, and the solid was dried under reduced pressure toobtain 0.95 g (1.43 mmol, 78% yield) of compound A-7 as a brown powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 6.90-7.90 (m,26H), 8.00 (s,2H)

FD-mass spectrometry: 662 (M+)

Elemental analysis: Ti: 6.5% (6.5)

C: 62.0% (62.2), H: 3.7% (3.8), N: 3.8% (3.8)

Calculated values in parentheses.

Synthesis Example 18

Synthesis of Compound B-7

After charging 1.0 g (3.66 mmol) of compound L7 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.48 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.84 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixture of zirconium tetrachloride (0.41 g,1.77 mmol) in 30 ml of diethyl ether cooled to −78° C. After completionof the dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, 20 ml of methylene chloride was added, and theinsoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreslurried with hexane. The slurry was filtered to remove the solventand the solid was dried under reduced pressure to obtain 0.94 g (1.33mmol, 73% yield) of compound B-7 as a yellow green powder represented bythe formula given below.

¹H-NMR(CDCl₃): 7.00-7.90 (m,26H), 8.20 (s,2H)

FD-mass spectrometry: 704 (M+)

Elemental analysis: Zr: 11.5% (11.7)

Calculated values in parentheses.

Synthesis Example 19

Synthesis of Compound A-8

After charging 1.0 g (2.93 mmol) of compound L8 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.10 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixture containing 2.9 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.45 mmol) and 20ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the reaction solution was filtered with a glassfilter. The filtrate was concentrated under reduced pressure, and thedeposited solid was reslurried with hexane. The slurry was filtered toremove the solvent and the solid was dried under reduced pressure toobtain 1.06 g (1.33 mmol, 91% yield) of compound A-8 as a brown powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 0.90-1.70 (m,18H), 3.40-3.80 (m,4H), 7.00-7.70 (m,20H),7.80-8.20 (m,2H)

FD-mass spectrometry: 798 (M+)

Elemental analysis: Ti: 6.0% (6.0)

Calculated value in parentheses.

Synthesis Example 20

Synthesis of Compound B-8

After charging 1.0 g (2.93 mmol) of compound L8 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.10 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixture of zirconium tetrachloride (0.34 g,1.44 mmol) in 20 ml of diethyl ether which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, 20 ml of diethyl ether wasadded, and the insoluble portion was removed with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reslurried with hexane. The slurry was filtered to remove thesolvent and the solid was dried under reduced pressure to obtain 1.02 g(1.21 mmol, 83% yield) of compound B-8 as a yellow green powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 0.90-1.80 (m,18H), 3.40-3.90 (m,4H), 6.40-7.90 (m,20H),8.00-8.30 (m,2H)

FD-mass spectrometry: 842 (M+)

Elemental analysis: Zr: 11.1% (10.8)

Calculated value in parentheses.

Synthesis Example 21

Synthesis of Compound A-9

After charging 0.50 g (1.23 mmol) of compound L9 and 15 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.84 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.30 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.2 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.60mmol) and 15 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the reaction solution was filtered witha glass filter. The filtrate was concentrated under reduced pressure,and the deposited solid was reslurried with hexane. The slurry wasfiltered to remove the solvent and the solid was dried under reducedpressure to obtain 0.33 g (0.36 mmol, 58% yield) of compound A-9 as abrown powder represented by the formula given below.

¹H-NMR(CDCl₃): 1.70-1.90 (m,18H), 6.60-7.80 (m,34H)

FD-mass spectrometry: 926 (M+)

Elemental analysis: Ti: 5.3% (5.2)

Calculated value in parentheses.

Synthesis Example 22

Synthesis of Compound B-9

After charging 0.50 g (1.23 mmol) of compound L9 and 15 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.84 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.30 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution of zirconiumtetrachloride (0.14 g, 0.60 mmol) and 15 ml of diethyl ether which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the solvent was distilled off, the resulting solid was dissolved in 50ml of methylene chloride and 10 ml of diethyl ether, and then theinsoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreslurried with hexane. The slurry was filtered to remove the solventand the solid was dried under reduced pressure to obtain 0.19 g (0.20mmol, 32% yield) of compound 3-9 as a light yellow powder represented bythe formula given below.

¹H-NMR(CDCl₃): 1.28-1.52 (m,18H), 6.70-7.76 (m,34H)

FD-mass spectrometry: 970 (M+)

Elemental analysis: Zr: 9.6% (9.4)

Calculated value in parentheses.

Synthesis Example 23

Synthesis of Compound A-10

After charging 0.32 g (1.03 mmol) of compound L10 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.77 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.19 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution containing 1.0 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 0.50 mmol) and 10ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the reaction solution was filtered with a glassfilter. The filtrate was concentrated under reduced pressure, and thedeposited solid was reprecipitated with methylene chloride and hexaneand dried under reduced pressure to obtain 0.16 g (0.22 mmol, 43% yield)of compound A-10 as a brown powder represented by the formula givenbelow.

¹H-NMR(CDCl₃): 0.40-0.90 (m,30H), 6.60-7.80 (m,18H)

FD-mass spectrometry: 739 (M+)

Elemental analysis: Ti: 5.3% (5.2)

Calculated value in parentheses.

Synthesis Example 24

Synthesis of Compound A-11

After charging 0.68 g (2.40 mmol) of compound L11 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.49 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.40 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution containing 2.4 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.20 mmol) and 15ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 15 hoursat room temperature, the solvent of the reaction solution was distilledoff, the resulting solid was dissolved in 50 ml of methylene chloride,and the insoluble portion was filtered off with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with methylene chloride and hexane at 0° C. anddried under reduced pressure to obtain 0.37 g (0.54 mmol, 45% yield) ofcompound A-11 as a red brown powder.

¹H-NMR(CDCl₃): 1.20-1.40 (m,9H), 1.50-1.55 (m,9H), 3.70-3.85 (m,6H),6.52-7.40 (m,14H), 8.05-8.20 (m,2H)

FD-mass spectrometry: 682 (M+)

Elemental analysis: Ti: 7.0% (7.0)

Calculated value in parentheses.

Synthesis Example 25

Synthesis of Compound B-11

After charging 0.64 g (2.26 mmol) of compound L11 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.40 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.26 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution of zirconium tetrachloride.2THF(0.42 g, 1.10 mmol) in 20 ml of tetrahydrofuran which had been cooled to−78° C. After completion of the dropwise addition, stirring wascontinued while slowly increasing the temperature to room temperature.After further stirring for 15 hours at room temperature, the solvent ofthe reaction solution was distilled off. The resulting solid wasdissolved in 50 ml of methylene chloride, and the insoluble portion wasfiltered off with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withmethylene chloride and hexane and dried under reduced pressure to obtain0.25 g (0.34 mmol, 31% yield) of compound B-11 as a yellow green powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 1.20-1.60 (m,18H), 3.66-3.86 (m,6H), 6.50-7.50 (m,14H),8.05-8.20 (m,2H)

FD-mass spectrometry: 726 (M+)

Elemental analysis: Zr: 12.4% (12.6)

Calculated value in parentheses.

Synthesis Example 26

Synthesis of Compound A-12

After charging 1.0 g (2.31 mmol) of compound L12 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.56 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.3 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.15mmol) and 20 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion was filtered offwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reslurried with hexane. The slurrywas filtered to remove the solvent and the solid was dried under reducedpressure to obtain 0.45 g (0.45 mmol, 40% yield) of compound A-12 as ared brown powder.

¹H-NMR(CDCl₃): 1.30-2.20 (m,24H), 6.20-7.40 (m,34H), 7.50-7.70 (m,2H)

FD-mass spectrometry: 982 (M+)

Elemental analysis: Ti: 5.0% (4.9)

Calculated value in parentheses.

Synthesis Example 27

Synthesis of Compound B-12

After charging 1.0 g (2.31 mmol) of compound L12 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.56 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution of zirconiumtetrachloride (0.27 g, 1.15 mmol) and 20 ml of diethyl ether which hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with diethyl ether, hexane, heptane and pentane,reslurried and washed, and then dried under reduced pressure to obtain0.02 g (0.02 mmol, 1% yield) of compound B-12 as a yellow green powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 1.20-2.10 (m,24H), 6.20-7.40 (m,34H), 7.50-8.00 (m,2H)

FD-mass spectrometry: 1026 (M+)

Elemental analysis: Zr: 9.1% (8.9)

Calculated value in parentheses.

Synthesis Example 28

Synthesis of Compound A-13

After charging 1.10 g (3.26 mmol) of compound L13 and 22 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.2 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.41 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 3.26 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.13mmol) and 22 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the solvent of the reaction solutionwas distilled off, the insoluble portion of the reaction solution wasfiltered off with a glass filter. The filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withdiethyl ether and pentane and dried under reduced pressure to obtain0.22 g (0.28 mmol, 17% yield) of compound A-13 as a red brown powder.

¹H-NMR(CDCl₃): 0.60-2.41 (m,44H), 6.70-7.60 (m,34H), 7.91-8.10 (m,2H)

FD-mass spectrometry: 790 (M+)

Elemental analysis: Ti: 6.3% (6.1)

Calculated value in parentheses.

Synthesis Example 29

Synthesis of Compound B-13

After charging 1.03 g (3.02 mmol) of compound L13 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.10 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution of zirconiumtetrachloride (0.35 g, 1.50 mmol) and 20 ml of diethyl ether that hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, the deposited solid wasrecrystallized with pentane and dried under reduced pressure to obtain0.27 g (0.32 mmol, 21% yield) of compound B-13 as a yellow green powderrepresented by the formula given below.

¹H-NMR (CDCl₃): 0.30-2.32 (m, 44H), 6.70-7.60 (m, 14H), 7.90-8.20 (m,2H)

FD-mass spectrometry: 834 (M+)

Elemental analysis: Zr: 10.9% (10.9)

Calculated value in parentheses.

Synthesis Example 30

Synthesis of Compound A-14

After charging 0.98 g (2.97 mmol) of compound L14 and 30 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 3.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.50mmol) and 15 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion of the reactionsolution was filtered off, the filtered substance was dissolved in 30 mlof diethyl ether and 50 ml of methylene chloride, and the insolubleportion was filtered off with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasrecrystallized with diethyl ether and dried under reduced pressure toobtain 0.66 g (0.85 mmol, 57% yield) of compound A-14 as a dark brownpowder.

¹H-NMR(CDCl₃): 1.41 (s,18H), 6.70-7.90 (m,24H), 8.18 (s,2H)

FD-mass spectrometry: 774 (M+)

Elemental analysis: Ti: 6.2% (6.2)

Calculated value in parentheses.

Synthesis Example 31

Synthesis of Compound B-14

After charging 1.01 g (3.05 mmol) of compound L14 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a tetrahydrofuran solution containingzirconium tetrachloride (0.36 g, 1.52 mmol) that had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 8 hours at room temperature, the insoluble portionwas removed with a glass filter. The filtrate was concentrated todryness, and the deposited solid was reprecipitated with methylenechloride and hexane and dried under reduced pressure to obtain 0.61 g(0.74 mmol, 49% yield) of compound B-14 as a fluorescent yellow powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 1.41 (s,18H), 6.80-7.90 (m,24H), 8.24 (s,2H)

FD-mass spectrometry: 818 (M+)

Elemental analysis: Zr: 11.0% (11.1)

Calculated value in parentheses.

Synthesis Example 32

Synthesis of Compound A-15

After charging 0.40 g (1.01 mmol) of compound L15 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.77 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.19 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.50mmol) and 10 ml of diethyl ether that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion was filtered offwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.19 g (0.21 mmol,42% yield) of compound A-15 as a red brown powder.

¹H-NMR(CDCl₃): 0.60-1.30 (m,6H), 6.50-7.80 (m,36H), 7.80-7.90 (m,2H)

FD-mass spectrometry: 900 (M+)

Elemental analysis: Ti: 5.5% (5.3)

Calculated value in parentheses.

Synthesis Example 33

Synthesis of Compound B-15

After charging 0.40 g (1.02 mmol) of compound L15 and 10 ml oftetrahydrofuran into a 100 ml reactor which had been adequately driedand substituted with argon, they were cooled to −78° C. and stirred.After dropwise adding 0.77 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.19 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. After cooling thesolution to −78° C., solid zirconium tetrachloride (0.12 g, 0.50 mmol)was added. After completion of the addition, stirring was continuedwhile slowly increasing the temperature to room temperature. Afterfurther stirring for 15 hours at room temperature, the solvent of thereaction solution was distilled off. The resulting solid was dissolvedin 50 ml of methylene chloride, and the insoluble portion was removedwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.20 g (0.21 mmol,42% yield) of compound B-15 as a grayish white powder represented by theformula given below.

¹H-NMR(CDCl₃): 0.70-1.00 (m,6H), 6.60-7.60 (m,36H), 7.70-7.80 (m,2H)

FD-mass spectrometry: 944 (M+)

Elemental analysis: Zr: 9.4% (9.6)

Calculated value in parentheses.

Synthesis Example 34

Synthesis of Compound A-16

After charging 1.0 g (4.73 mmol) of compound L16 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.2 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 4.96 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 4.7 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 2.35mmol) and 20 ml of diethyl ether that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filtered,and the filtered substance was dissolved in 50 ml of methylene chloride.The insoluble portion was removed, the filtrate was concentrated underreduced pressure, and the deposited solid was reprecipitated withmethylene chloride and hexane and dried under reduced pressure to obtain0.96 g (1.78 mmol, 75% yield) of compound A-16 as a pale brown powder.

¹H-NMR(CDCl₃): 1.90 (s,6H), 6.50-7.30 (m,16H), 7.90 (s,2H)

FD-mass spectrometry: 538 (M+)

Elemental analysis: Ti: 9.0% (8.9)

Calculated value in parentheses.

Synthesis Example 35

Synthesis of Compound B-16

After charging 1.0 g (4.73 mmol) of compound L16 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.2 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 4.96 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.55g, 2.36 mmol) and 20 ml of diethyl ether that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered off. The solvent of the filtrate was distilled off, and theresulting solid was recrystallized with diethyl ether, methylenechloride and hexane and dried under reduced pressure to obtain 0.49 g(0.84 mmol, 36% yield) of compound B-16 as a yellow green powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 2.00 (s,6H), 6.40-7.40 (m,16H), 8.10 (s,2H)

FD-mass spectrometry: 582 (M+)

Elemental analysis: Zr: 15.9% (15.7)

Calculated value in parentheses.

Synthesis Example 36

Synthesis of Compound A-17

After charging 1.0 g (2.77 mmol) of compound L17 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.87 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.90 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.76 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.38mmol) and 20 ml of diethyl ether that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the insoluble portion was filtered offwith a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reslurried with hexane. The slurrywas filtered to remove the solvent and the solid was dried under reducedpressure to obtain 0.15 g (0.18 mmol, 13% yield) of compound A-17 as abrown powder.

¹H-NMR(CDCl₃): 3.20-3.80 (m,4H), 6.90-7.81 (m,30H), 8.15 (s,2H)

FD-mass spectrometry: 838 (M+)

Elemental analysis: Ti: 5.9% (5.7)

Calculated value in parentheses.

Synthesis Example 37

Synthesis of Compound B-17

After charging 1.0 g (2.77 mmol) of compound L17 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.87 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.90 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.32g, 1.37 mmol) and 20 ml of diethyl ether that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the insoluble portion in thereaction solution was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreslurried with hexane. The slurry was filtered to remove the solventand the solid was dried under reduced pressure to obtain 0.71 g (0.88mmol, 58% yield) of compound B-17 as a yellow green powder representedby the formula given below.

¹H-NMR(CDCl₃): 3.30-3.80 (m,4H), 6.71-7.72 (m,30H), 8.25 (s,2H)

FD-mass spectrometry: 882 (M+)

Elemental analysis: Zr: 10.6% (10.3)

Calculated value in parentheses.

Synthesis Example 38

Synthesis of Compound A-18

After charging 0.59 g (2.20 mmol) of compound L18 and 10 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.49 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.31 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.2 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.10mmol) and 10 ml of tetrahydrofuran that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the mixture was concentrated todryness, and the resulting solid was dissolved in 20 ml of methylenechloride. The insoluble portion was filtered off with a glass filter,the filtrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with diethyl ether and hexane at −78° C. anddried under reduced pressure to obtain 0.27 g (0.41 mmol, 37% yield) ofcompound A-18 as a brown powder.

¹H-NMR(CDCl₃): 1.22 (s,18H), 2.40 (s,6H), 6.44-7.80 (m,14H), 8.21 (s,2H)

FD-mass spectrometry: 650 (M+)

Elemental analysis: Ti: 7.1% (7.4)

Calculated value in parentheses.

Synthesis Example 39

Synthesis of Compound B-18

After charging 0.60 g (2.25 mmol) of compound L18 and 10 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.26 g,1.12 mmol) in 10 ml of tetrahydrofuran that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, the solvent of the reactionsolution was distilled off. The resulting solid was dissolved in 20 mlof methylene chloride, and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.16 g (0.24 mmol, 21% yield) ofcompound B-18 as a yellow green powder represented by the formula givenbelow.

¹H-NMR(CDCl₃): 1.13 (s,18H), 2.39 (s,6H), 6.50-7.75 (m,14H), 8.26 (s,2H)

FD-mass spectrometry: 694 (M+)

Elemental analysis: Zr: 13.1% (13.1)

Calculated value in parentheses.

Synthesis Example 40

Synthesis of Compound B-19

After charging 0.70 g (2.25 mmol) of compound L19 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.26 g,1.12 mmol) in 10 ml of tetrahydrofuran that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the solvent of the reactionsolution was distilled off. The resulting solid was dissolved in 20 mlof methylene chloride, and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.16 g (0.20 mmol, 18% yield) ofcompound B-19 as a yellow green powder represented by the formula givenbelow.

¹H-NMR(CDCl₃): 1.43 (s,18H), 1.47 (s,18H), 6.90-7.60 (m,14H) 8.40 (s,2H)

FD-mass spectrometry: 778 (M+)

Elemental analysis: Zr: 12.1% (11.7)

Calculated value in parentheses.

Synthesis Example 41

Synthesis of Compound B-20

After charging 0.63 g (2.25 mmol) of compound L20 and 10 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.26 g,1.12 mmol) in 10 ml of tetrahydrofuran which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the solvent of the reactionsolution was distilled off. The resulting solid was dissolved in 25 mlof methylene chloride, and the insoluble portion was removed with aglass filter. The filtrate was concentrated under reduced pressure, andthe deposited solid was reprecipitated with diethyl ether and hexane anddried under reduced pressure to obtain 0.35 g (0.48 mmol, 43% yield) ofcompound B-20 as a yellow powder represented by the formula given below.

¹H-NMR(CDCl₃): 1.40 (s,18H), 1.50 (s,18H), 2.21 (s,12H) 6.70-7.40(m,12H), 8.33 (s,2H)

FD-mass spectrometry: 720 (M+)

Elemental analysis: Zr: 12.8% (12.6)

Calculated value in parentheses.

Synthesis Example 42

Synthesis of Compound A-21

After charging 0.80 g (2.50 mmol) of compound L21 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.7 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.64 mmol) over 5 minutes, the temperature was slowlyincreased to 0° C., and stirring was continued for 4 hours at 0° C. toprepare a lithium salt solution. The solution was then slowly addeddropwise to a mixed solution containing 2.5 ml of a titaniumtetrachloride solution (0.5 mmol/ml heptane solution, 1.25 mmol) and 10ml of diethyl ether which had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the mixture was concentrated to dryness, and theresulting solid was dissolved in 50 ml of diethyl ether and 60 ml ofmethylene chloride. The insoluble portion was filtered off with a glassfilter, the filtrate was concentrated under reduced pressure, and thedeposited solid was recrystallized with diethyl ether and dried underreduced pressure to obtain 0.07 g (0.09 mmol, 8% yield) of compound A-21as a red brown powder.

¹H-NMR(CDCl₃): 1.34 (s,18H), 6.75-7.75 (m,14H), 8.10 (s,2H)

FD-mass spectrometry: 758 (M+)

Elemental analysis: Ti: 6.5% (6.3)

Calculated value in parentheses.

Synthesis Example 43

Synthesis of Compound B-21

After charging 1.03 g (3.20 mmol) of compound L21 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.0 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to −15° C. and stirring was continued for 2 hours at −15° C.to prepare a lithium salt solution. The solution was then added dropwiseto a solution of zirconium tetrachloride (0.36 g, 1.54 mmol) in 10 ml oftetrahydrofuran which had been cooled to −78° C. After completion of thedropwise addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 15 hours atroom temperature, the solvent of the reaction solution was distilledoff. The residue was dissolved in 20 ml of toluene, and the reaction wascontinued for 3 hours under reflux conditions. The solvent was distilledoff, the resulting solid was dissolved in 50 ml of methylene chloride,and the insoluble portion was removed with a glass filter. The filtratewas concentrated under reduced pressure, and the deposited solid wasreprecipitated with diethyl ether and hexane and dried under reducedpressure to obtain 0.33 g (0.41 mmol, 27% yield) of compound B-21 as anocher powder represented by the formula given below.

¹H-NMR(CDCl₃): 1.24 (s,18H), 6.80-7.78 (m,14H), 8.15 (s,2H)

FD-mass spectrometry: 802 (M+)

Elemental analysis: Zr: 11.7% (11.4)

Calculated value in parentheses.

Synthesis Example 44

Synthesis of Compound A-22

After charging 0.50 g (1.77 mmol) of compound L22 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.86 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.77 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.89mmol) and 50 ml of diethyl ether which had been cooled to −78° C.

After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter. After washing the filtered substance withdiethyl ether, it was dissolved in methylene chloride. The insolubleportion was removed, the filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane at −78° C. and dried under reduced pressure to obtain 0.31 g(0.45 mmol, 51% yield) of compound A-22 as a brown powder.

¹H-NMR(CDCl₃): 0.70-1.80 (m,18H), 3.50-4.00 (m,6H), 6.40-7.70 (m,14H),8.05 (s,2H)

FD-mass spectrometry: 682 (M+)

Elemental analysis: Ti: 7.3% (7.0)

Calculated value in parentheses.

Synthesis Example 45

Synthesis of Compound B-22

After charging 0.50 g (1.77 mmol) of compound L22 and 25 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.86 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.21g, 0.99 mmol) in 10 ml of diethyl ether and 60 ml of tetrahydrofuranwhich had been cooled to −78° C. After completion of the dropwiseaddition, stirring was continued while slowly increasing the temperatureto room temperature. After further stirring for 15 hours at roomtemperature, the solvent of the reaction solution was distilled off. Theresulting solid was reslurried with 70 ml of hexane, and the insolubleportion was separated off with a glass filter. The filtered substancewas dissolved in 100 ml of diethyl ether and 70 ml of hexane. Afterremoving out the insoluble portion, the filtrate was concentrated underreduced pressure. The deposited solid was washed with hexane and driedunder reduced pressure to obtain 0.08 g (0.11 mmol, 11% yield) ofcompound B-22 as a yellow green powder represented by the formula givenbelow.

¹H-NMR(CDCl₃): 1.40 (s,18H), 3.75 (s,6H), 6.40-7.70 (m,14H), 8.10 (s,2H)

FD-mass spectrometry: 726 (M+)

Elemental analysis: Zr: 12.3% (12.6)

Calculated value in parentheses.

Synthesis Example 46

Synthesis of Compound A-23

After charging 1.01 g (4.33 mmol) of compound L23 and 22 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.9 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 4.50 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 4.25 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 2.13mmol) and 20 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filtered,the filtrate was concentrated to dryness, and the resulting solid wasreprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.26 g (0.44 mmol, 21% yield) ofcompound A-23 as a brown powder.

¹H-NMR(CDCl₃): 0.82-1.40 (m,12H), 2.90-3.30 (m,2H), 6.60-7.40 (m,16H),8.10 (s,2H)

FD-mass spectrometry: 594 (M+)

Elemental analysis: Ti: 8.0% (8.0)

Calculated value in parentheses.

Synthesis Example 47

Synthesis of Compound B-23

After charging 1.02 g (4.25 mmol) of compound L23 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.43 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 5.32 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.50g, 2.15 mmol) and 20 ml of diethyl ether that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the insoluble portion wasremoved with a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl ether,methylene chloride and hexane and dried under reduced pressure to obtain0.61 g (0.96 mmol, 45% yield) of compound B-23 as a yellow green powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 0.80-1.30 (m,12H), 2.90-3.25 (m,2H), 6.72-7.43 (m,16H),8.20 (s,2H)

FD-mass spectrometry: 638 (M+)

Elemental analysis: Zr: 14.0% (14.3)

Calculated value in parentheses.

Synthesis Example 48

Synthesis of Compound A-24

After charging 0.52 g (2.05 mmol) of compound L24 and 40 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.36 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.11 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt slurry. The solution wasslowly added dropwise to a mixed solution containing 2.04 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.02mmol), 40 ml of diethyl ether and 20 ml of tetrahydrofuran that had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature,the solvent of the reaction solution was distilled off. The resultingsolid was reslurried with 100 ml of diethyl ether, and the insolubleportion was separated off with a glass filter. The filtered substancewas washed with diethyl ether and dissolved in methylene chloride. Afterremoving the insoluble portion, the filtrate was concentrated underreduced pressure, and the deposited solid was washed with hexane anddried under reduced pressure to obtain 0.12 g (0.19 mmol, 19% yield) ofcompound A-24 as an orange powder.

¹H-NMR(CDCl₃): 0.80-2.30 (m,18H), 6.30-9.20 (m,14H), 8.35 (brs,2H)

FD-mass spectrometry: 624 (M+)

Elemental analysis: Ti: 8.1% (7.7)

Calculated value in parentheses.

Synthesis Example 49

Synthesis of Compound B-24

After charging 0.76 g (2.99 mmol) of compound L24 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.91 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 3.08 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt slurry. The solution was thenadded dropwise to a mixed solution of zirconium tetrachloride.2THFcomplex (0.563 g, 1.49 mmol) in 80 ml of tetrahydrofuran which had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 15 hours at room temperature, 50ml of toluene was added, and the reaction solution was heated at 80° C.for 10 hours and then at 90° C. for 30 hours while stirring. The solventof the reaction solution was distilled off, the resulting solid wasreslurried with 150 ml of diethyl ether, and the insoluble portion wasseparated off with a glass filter. After washing the filtered substancewith diethyl ether, it was dissolved in methylene chloride, theinsoluble portion was removed out, and then the filtrate wasconcentrated under reduced pressure. The deposited solid was washed withhexane and dried under reduced pressure to obtain 0.43 g (0.64 mmol, 43%yield) of compound B-24 as a yellow powder represented by the formulagiven below.

¹H-NMR(CDCl₃): 0.60-2.30 (m,18H), 6.30-9.40 (m,14H), 8.35 (brs, 2H)

FD-mass spectrometry: 668 (M+)

Elemental analysis: Zr: 13.2% (13.6)

Calculated value in parentheses.

Synthesis Example 50

Synthesis of Compound A-25

After charging 0.50 g (1.93 mmol) of compound L25 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.42 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.20 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasslowly added dropwise to a mixed solution containing 1.93 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.97mmol) and 50 ml of diethyl ether that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 15 hours at room temperature, the reaction solution was filteredwith a glass filter, and the filtered substance was washed with diethylether and dissolved in methylene chloride. After removing the insolubleportion, the filtrate was concentrated under reduced pressure, and thedeposited solid was washed with hexane and dried under reduced pressureto obtain 0.11 g (0.17 mmol, 18% yield) of compound A-25 as a red brownpowder.

¹H-NMR(CDCl₃): 1.65 (s,18H), 0.50-2.40 (m,20H), 3.85 (brdt,2H),6.90-7.70 (m,6H), 8.20 (s,2H)

FD-mass spectrometry: 634 (M+)

Elemental analysis: Ti: 7.6% (7.5)

Calculated value in parentheses.

Synthesis Example 51

Synthesis of Compound B-25

After charging 0.50 g (1.93 mmol) of compound L25 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.42 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.20 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.23 g,0.99 mmol) in 50 ml of diethyl ether which had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 15 hours at room temperature, the reaction solution wasfiltered with a glass filter, and the filtrate was concentrated underreduced pressure. The deposited solid was washed with hexane and driedunder reduced pressure to obtain 0.28 g (0.41 mmol, 43% yield) ofcompound B-25 as an ocher powder represented by the formula given below.

¹H-NMR(CDCl₃): 1.65 (s,18H), 0.70-2.50 (m,20H), 3.85 (brdt,2H),6.70-7.70 (m,6H), 8.25 (s,2H)

FD-mass spectrometry: 678 (M+)

Elemental analysis: Zr: 13.3% (13.4)

Calculated value in parentheses.

Synthesis Example 52

Synthesis of Compound A-26

After charging 0.61 g (2.28 mmol) of compound L26 and 10 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.6 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.48 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.2 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.10mmol) and 10 ml of tetrahydrofuran that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 12 hours at room temperature, the insoluble portion was filtered outwith a glass filter, the filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane at −78° C. and dried under reduced pressure to obtain 0.36 g(0.55 mmol, 51% yield) of compound A-26 as a brown powder.

¹H-NMR(CDCl₃): 1.33 (s,18H), 2.14 (s,6H), 6.60-7.68 (m,14H), 8.03 (s,2H)

FD-mass spectrometry: 650 (M+)

Elemental analysis: Ti: 7.4% (7.3)

Calculated value in parentheses.

Synthesis Example 53

Synthesis of Compound B-26

After charging 0.61 g (2.28 mmol) of compound L26 and 10 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.6 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 2.48 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.27 g,1.15 mmol) in 10 ml of diethyl ether that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the insoluble portion wasremoved with a glass filter. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with diethyl etherand hexane and dried under reduced pressure to obtain 0.14 g (0.20 mmol,18% yield) of compound B-26 as a yellow green powder represented by theformula given below.

¹H-NMR(CDCl₃): 1.31 (s,18H), 2.14 (s,6H), 6.69-7.65 (m,14H), 8.09 (s,2H)

FD-mass spectrometry: 694 (M+)

Elemental analysis: Zr: 13.1% (13.1)

Calculated value in parentheses.

Synthesis Example 54

Synthesis of Compound A-27

After charging 0.30 g (1.00 mmol) of compound L27 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.65 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.00 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.0 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.50mmol) and 10 ml of diethyl ether that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After first stirring for12 hours at room temperature and then stirring for one hour underreflux, the insoluble portion was filtered out with a glass filter. Thefiltrate was concentrated under reduced pressure, and the depositedsolid was reprecipitated with diethyl ether and hexane and dried underreduced pressure to obtain 0.18 g (0.25 mmol, 50% yield) of compoundA-27 as an orange powder.

¹H-NMR(CDCl₃): 1.13 (s,18H), 1.25 (brd,6H), 1.28 (brd,6H), 3.29(brdq,2H), 6.45-6.70 (m,2H), 6.80-7.20 (m,4H), 7.20-7.50 (m,8H), 8.23(s,2H)

FD-mass spectrometry: 706 (M+)

Elemental analysis: Ti: 6.8% (6.8)

Calculated value in parentheses.

Synthesis Example 55

Synthesis of Compound B-27

After charging 0.95 g (3.20 mmol) of compound L27 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.08 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 3.22 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride (0.37 g,1.60 mmol) in 10 ml of tetrahydrofuran that had been cooled to −78° C.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After firststirring for 12 hours at room temperature and then stirring for 6 hoursunder reflux, the solvent of the reaction solution was distilled off.The resulting solid was dissolved in 50 ml of methylene chloride, andthe insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with methylene chloride and hexane and dried underreduced pressure to obtain 0.18 g (0.24 mmol, 15% yield) of compoundB-27 as a yellow powder.

¹H-NMR(CDCl₃): 1.10 (s,18H), 1.10-1.40 (m,12H), 3.20-3.30 (m,2H),6.30-6.60 (m,2H), 6.70-7.10-7.60 (m,8H), 8.28 (s,2H)

FD-mass spectrometry: 750 (M+)

Elemental analysis: Zr: 12.0% (12.2)

C: 63.5% (64.0) H: 6.6% (6.4) N: 3.5% (3.7)

Calculated values in parentheses.

Synthesis Example 56

Synthesis of Compound A-28

After charging 0.50 g (1.37 mmol) of compound L28 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.92 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.43 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.37 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane, 0.69 mmol) and 40ml of diethyl ether that had been cooled to −78° C. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the reaction solution was filtered with a glassfilter, the filtered substance was washed with diethyl ether, and thenthe insoluble portion was removed out by filtration. The filtrate wasconcentrated under reduced pressure, and the deposited solid was washedwith hexane and dried under reduced pressure to obtain 0.17 g (0.20mmol, 29% yield) of compound A-28 as a brown powder.

¹H-NMR(CDCl₃): 0.70-1.40 (m,54H), 6.65-7.75 (m,12H), 8.35 (s,2H)

FD-mass spectrometry: 846 (M+)

Elemental analysis: Ti: 5.5% (5.7)

Calculated value in parentheses.

Synthesis Example 57

Synthesis of Compound B-28

After charging 0.50 g (1.37 mmol) of compound L28 and 40 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 0.92 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.43 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution of zirconium tetrachloride (0.16g, 0.69 mmol) in 20 ml of anhydrous diethyl ether and 50 ml oftetrahydrofuran that had been cooled to −78° C. After completion of thedropwise addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 12 hours atroom temperature, the solvent of the reaction solution was distilledoff. The resulting solid was reslurried with diethyl ether, theinsoluble portion was removed off with a glass filter, and the filtratewas concentrated under reduced pressure. The deposited solid wasreprecipitated with hexane at −78° C. and dried under reduced pressureto obtain 0.26 g (0.29 mmol, 43% yield) of compound B-28 as a yellowpowder represented by the formula given below.

¹H-NMR(CDCl₃): 0.80-1.30 (m,54H), 6.65 (m,12H), 8.35 (s,2H)

FD-mass spectrometry: 890 (M+)

Elemental analysis: Zr: 9.9% (10.2)

Calculated value in parentheses.

Synthesis Example 58

Synthesis of Compound A-29

After charging 0.60 g (1.79 mmol) of compound L29 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.17 ml of n-butyllithium (1.55 mmol/ml n-hexanesolution, 1.81 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 1.79 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.90mmol) and 50 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After stirring for 12hours at room temperature, the reaction solution was filtered with aglass filter to remove the insoluble portion. The filtrate wasconcentrated under reduced pressure, and the deposited solid was washedwith hexane and dried under reduced pressure to obtain 0.10 g (0.13mmol, 14% yield) of compound A-29 as a red brown powder.

¹H-NMR(CDCl₃): 0.80-2.30 (m,20H), 1.55 (s,18H), 3.65 (brdt,2H),6.60-8.10 (m,16H)

FD-mass spectrometry: 786 (M+)

Elemental analysis: Ti: 6.4% (6.1)

Calculated value in parentheses.

Synthesis Example 59

Synthesis of Compound B-29

After charging 0.50 g (1.48 mmol) of compound L29 and 40 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.02 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.64 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride.2THFcomplex (0.26 g, 0.69 mmol) in 40 ml of tetrahydrofuran that had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, 70ml of toluene was added, the reaction solution was heated at 80° C. for20 hours while stirring. The solvent of the reaction solution wasdistilled off, the resulting solid was reslurried with 50 ml of diethylether. The slurry was filtered with a glass filter to remove off theinsoluble portion, and then the filtrate was concentrated under reducedpressure. The deposited solid was reprecipitated with hexane at −78° C.and dried under reduced pressure to obtain 0.04 g (0.05 mmol, 7% yield)of compound B-29 as a yellowish white powder represented by the formulagiven below.

¹H-NMR(CDCl₃): 0.90-1.90 (m,20H), 1.55 (s,18H), 3.25 (brdt,2H),6.40-7.90 (m,16H)

FD-mass spectrometry: 830 (M+)

Elemental analysis: Zr: 11.3% (11.0)

Calculated value in parentheses.

Synthesis Example 60

Synthesis of Compound A-30

After charging 0.51 g (1.86 mmol) of compound L30 and 50 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a solution containing 1.85 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.93mmol) and 60 ml of tetrahydrofuran that had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. Further stirring for 8hours at room temperature, the reaction solution was heated at 60° C.for 8 hours while stirring, and the solvent was then distilled off. Theresulting solid was reslurried with diethyl ether and filtered with aglass filter, and the filtered substance was washed with diethyl etherand then dissolved in methylene chloride. After removal of the insolubleportion by filtration, the filtrate was concentrated under reducedpressure, and the deposited solid was washed with hexane and dried underreduced pressure to obtain 0.14 g (0.21 mmol, 23% yield) of compoundA-30 as a red orange powder.

¹H-NMR(CDCl₃): 1.10-2.10 (m,20H), 1.45 (s,18H), 2.40 (s,6H), 3.85(brdt,2H), 6.70-7.70 (m,6H)

FD-mass spectrometry: 662 (M+)

Elemental analysis: Ti: 7.1% (7.2)

Calculated value in parentheses.

Synthesis Example 61

Synthesis of Compound B-30

After charging 0.51 g (1.86 mmol) of compound L30 and 50 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasadded dropwise to a solution of zirconium tetrachloride (0.22 g, 0.94mmol) in 60 ml of tetrahydrofuran which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 12 hours at room temperature, 60 ml of toluene was added, and thereaction solution was heated at 85° C. for 12 hours while stirring.

The solvent of the reaction solution was distilled off. The resultingsolid was reslurried with 100 ml of diethyl ether, the slurry wasfiltered with a glass filter to remove off the insoluble portion, andthen the filtrate was concentrated under reduced pressure. The depositedsolid was washed with hexane and dried under reduced pressure to obtain0.10 g (0.14 mmol, 15% yield) of compound B-30 as a milky white powderrepresented by the formula given below.

¹H-NMR(CDCl₃): 0.80-2.10 (m,20H), 1.45 (s,18H), 2.40 (s,6H), 3.75(brdt,2H), 6.50-7.80 (m,6H)

FD-mass spectrometry: 704 (M+)

Elemental analysis: Zr: 13.3% (12.9)

Calculated value in parentheses.

Synthesis Example 62

Synthesis of Compound A-31

After charging 1.00 g (4.22 mmol) of compound L31 and 20 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.75 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 4.43 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 4.22 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 2.11mmol) and 20 ml of diethyl ether that had been cooled to −78° C.

After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After stirringfor 12 hours at room temperature, the reaction solution was filteredwith a glass filter. The filtered substance was dissolved in 50 ml ofmethylene chloride, and the insoluble portion was removed. The filtratewas evaporated to dryness under reduced pressure, and the resultingsolid was reprecipitated with methylene chloride and diethyl ether anddried under reduced pressure to obtain 0.90 g (1.55 mmol, 72% yield) ofcompound A-31 as a brown powder.

¹H-NMR(CDCl₃): 6.70-7.40 (m,16H), 7.90-8.20 (m,2H)

FD-mass spectrometry: 578 (M+)

Elemental analysis: Ti: 8.0% (8.3)

Calculated value in parentheses.

Synthesis Example 63

Synthesis of Compound B-31

After charging 1.20 g (5.18 mmol) of compound L31 and 24 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.38 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 5.44 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a mixed solution containing zirconiumtetrachloride (0.60 g, 2.57 mmol) and 24 ml of diethyl ether that hadbeen cooled to −78° C. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After stirring for 12 hours at room temperature, thereaction solution was filtered with a glass filter. The filteredsubstance was dissolved in 60 ml of methylene chloride and the insolubleportion was removed. The filtrate was concentrated under reducedpressure, and the deposited solid was reprecipitated with methylenechloride and hexane and dried under reduced pressure to obtain 0.20 g(0.32 mmol, 12% yield) of compound B-31 as a green powder.

¹H-NMR(CDCl₃): 6.70-7.45 (m,16H), 7.90-8.25 (m,2H)

FD-mass spectrometry: 621 (M+)

Elemental analysis: Zr: 14.9% (14.6)

Calculated value in parentheses.

Synthesis Example 64

Synthesis of Compound A-32

After charging 1.00 g (5.05 mmol) of compound L32 and 50 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 3.25 ml of n-butyllithium (1.63 mmol/ml n-hexanesolution, 5.30 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 2.52 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 1.26 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the reaction solution wasfiltered with a glass filter and the filtered substance was washed withdiethyl ether followed by dissolution in methylene chloride. Afterremoval of the insoluble portion, the filtrate was concentrated underreduced pressure, and the deposited solid was washed with hexane anddried under reduced pressure to obtain 0.23 g (0.45 mmol, 18% yield) ofcompound A-32 as an orange powder.

FD-mass spectrometry: 512 (M+)

Synthesis Example 65

Synthesis of compound A-33

After charging 1.09 g (4.39 mmol) of compound L33 and 70 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.80 ml of n-butyllithium (1.63 mmol/ml n-hexanesolution, 4.56 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 8.78 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 4.39 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 12 hours at room temperature, the reaction solution wasfiltered with a glass filter and the filtered substance was washed withdiethyl ether followed by dissolution in methylene chloride. Afterremoval of the insoluble portion, the filtrate was concentrated underreduced pressure, and the deposited solid was washed with diethyl etherand dried under reduced pressure to obtain 0.22 g (0.36 mmol, 16% yield)of compound A-33 as a brown powder.

FD-mass spectrometry: 612 (M+)

Synthesis Example 66

Synthesis of Compound A-34

After charging 0.60 g (2.13 mmol) of compound L34 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 2.75 ml of n-butyllithium (1.63 mmol/ml n-hexanesolution, 4.48 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wascooled to −78° C., and then 0.71 g (2.13 mmol) of a titaniumtetrachloride-tetrahydrofuran complex was slowly added. After completionof the addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 8 hours atroom temperature, the reaction solution was filtered with a glass filterand the filtered substance was washed with diethyl ether followed bydissolution in methylene chloride. After removal of the insolubleportion, the filtrate was concentrated under reduced pressure, and thedeposited solid was washed with hexane and dried under reduced pressureto obtain 0.19 g (0.48 mmol, 23% yield) of compound A-34 as a redpowder.

FD-mass spectrometry: 398 (M+)

Synthesis Example 67

Synthesis of compound A-35

After charging 0.19 g of sodium hydride (60 wt % product, 4.75 mmol) and50 ml of tetrahydrofuran into a 100 ml reactor which had been adequatelydried and substituted with argon, a solution of 1.00 g (2.30 mmol) ofcompound L35 in 20 ml of tetrahydrofuran was added dropwise over 5minutes while stirring at room temperature, after which the temperaturewas slowly increased to room temperature, and stirring was continued for2 hours at 50° C. to prepare a sodium salt solution. The solution wasthen slowly added dropwise to a solution of 0.77 g (2.31 mmol) of atitanium tetrachloride-tetrahydrofuran complex in 50 ml oftetrahydrofuran while stirring at room temperature. After completion ofthe dropwise addition, stirring was continued while slowly increasingthe temperature to room temperature. After further stirring for 8 hoursat room temperature, the reaction solution was filtered with a glassfilter and the filtered substance was washed with diethyl ether followedby removal of the insoluble portion. The filtrate was concentrated underreduced pressure, the deposited solid was reslurried with diethyl ether,the reaction solution was filtered with a glass filter. The filteredsubstance was washed with diethyl ether and dissolved in methylenechloride, and the impurities were removed. The filtrate was concentratedunder reduced pressure, and the deposited solid was washed with hexaneand dried under reduced pressure to obtain 1.10 g (2.00 mmol, 87% yield)of compound A-35 as a red orange powder.

FD-mass spectrometry: 550 (M+)

Synthesis Example 68

Synthesis of Compound A-36

After charging 0.19 g of sodium hydride (60 wt % product, 4.75 mmol) and50 ml of tetrahydrofuran into a 100 ml reactor which had been adequatelydried and substituted with argon, a solution of 1.00 g (2.23 mmol) ofcompound L36 in 20 ml of tetrahydrofuran was added dropwise over 5minutes while stirring at room temperature, after which the temperaturewas slowly increased to room temperature, and stirring was continued for2 hours at 50° C. to prepare a sodium salt solution. The solution wascooled to −78° C., and then 4.50 ml of a titanium tetrachloride solution(0.5 mmol/ml heptane solution, 2.25 mmol) was slowly added dropwise.After completion of the dropwise addition, stirring was continued whileslowly increasing the temperature to room temperature. After furtherstirring for 8 hours at room temperature, the reaction solution wasfiltered with a glass filter and the filtered substance was washed withdiethyl ether and dissolved in methylene chloride. After removal of theinsoluble portion, the filtrate was concentrated under reduced pressure,and the deposited solid was washed with hexane and dried under reducedpressure to obtain 0.55 g (0.97 mmol, 44% yield) of compound A-36 as anorange powder.

FD-mass spectrometry: 564 (M+)

Synthesis Example 69

Synthesis of Compound B-37

After charging 0.30 g of sodium hydride (60 wt % product, 7.50 mmol) and50 ml of tetrahydrofuran into a 100 ml reactor which had been adequatelydried and substituted with argon, a solution of 1.00 g (3.16 mmol) ofcompound L37 in 20 ml of tetrahydrofuran was added dropwise over 5minutes while stirring at room temperature, after which the temperaturewas slowly increased to room temperature, and stirring was continued for2 hours at 60° C. to prepare a sodium salt solution. The solution wasthen slowly added dropwise to a solution of 1.19 g (3.15 mmol) ofzirconium tetrachloride.2THF complex in 50 ml of tetrahydrofuran whilestirring at room temperature. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, thereaction solution was filtered with a glass filter, the filteredsubstance was washed with tetrahydrofuran and the insoluble portion wasremoved. The filtrate was concentrated under reduced pressure to about⅓, the deposited solid was filtered with a glass filter, and thefiltered substance was washed with cold tetrahydrofuran and dried underreduced pressure to obtain 1.00 g (2.10 mmol, 66% yield) of compoundB-37 as a yellow powder.

FD-mass spectrometry: 474 (M+)

Synthesis Example 70

Synthesis of Compound B-38

After charging 0.23 g of sodium hydride (60 wt % product, 5.75 mmol) and50 ml of tetrahydrofuran into a 100 ml reactor which had been adequatelydried and substituted with argon, a solution of 1.00 g (2.73 mmol) ofcompound L38 in 20 ml of tetrahydrofuran was added dropwise over 5minutes while stirring at room temperature, after which the temperaturewas slowly increased to room temperature, and stirring was continued for2 hours at 50° C. to prepare a sodium salt solution. The solution wasthen slowly added dropwise to a solution of 1.03 g (2.73 mmol) ofzirconium tetrachloride.2THF complex in 50 ml of tetrahydrofuran whilestirring at room temperature. After completion of the dropwise addition,stirring was continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, thereaction solution was filtered with a glass filter, the filteredsubstance was washed with tetrahydrofuran and the insoluble portion wasremoved by filtration. The filtrate was allowed to stand for 2 hours,upon which a solid was deposited. The deposited solid was filtered witha glass filter, and the filtered substance was washed with coldtetrahydrofuran and dried under reduced pressure to obtain 1.15 g (2.18mmol, 80% yield) of compound B-38 as a yellow powder.

FD-mass spectrometry: 524 (M+)

Synthesis Example 71

Synthesis of Compound A-39

After charging 0.50 g (1.87 mmol) of compound L39 and 50 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasslowly added dropwise to a mixed solution containing 1.87 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 0.94mmol) and 70 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the reaction solution was filtered witha glass filter, and the filtered substance was washed with diethyl etherand then dissolved in methylene chloride. The insoluble portion wasremoved, the filtrate was then concentrated under reduced pressure, andthe deposited solid was washed with hexane and dried under reducedpressure to obtain 0.11 g (0.17 mmol, 18% yield) of compound A-39 as ared powder.

¹H-NMR(CDCl₃): 1.65 (s,18H), 4.65 (d,2H), 5.00 (d,2H), 6.75-7.70(m,16H), 7.75 (s,2H)

FD-mass spectrometry: 650 (M+)

Elemental analysis: Ti: 7.2% (7.3)

Calculated value in parentheses.

Synthesis Example 72

Synthesis of Compound B-39

After charging 0.50 g (1.87 mmol) of compound L39 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.20 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 1.93 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride.2THFcomplex (0.352 g, 0.93 mmol) in 50 ml of tetrahydrofuran that had beencooled to −78° C. After completion of the dropwise addition, stirringwas continued while slowly increasing the temperature to roomtemperature. After further stirring for 8 hours at room temperature, thereaction solution was heated at 60° C. for 3 hours while stirring, andthe solvent was then distilled off. The resulting solid was reslurriedwith 50 ml of diethyl ether and the insoluble portion was separated offwith a glass filter. The filtered substance was washed with 100 ml ofdiethyl ether and dissolved in methylene chloride, the insoluble portionwas removed off, and the filtrate was concentrated under reducedpressure. The deposited solid was washed with hexane and dried underreduced pressure to obtain 0.30 g (0.43 mmol, 46% yield) of compoundB-39 as a yellowish white powder represented by the formula given below.

¹H-NMR(CDCl₃): 1.60 (s,18H), 4.65 (d,2H), 4.95 (d,2H), 6.70-7.70(m,16H), 7.85 (s,2H)

FD-mass spectrometry: 694 (M+)

Elemental analysis: Zr: 12.9% (13.1)

Calculated value in parentheses.

Synthesis Example 73

Synthesis of Compound A-40

After charging 0.58 g (2.02 mmol) of compound L40 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.50 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.00 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.00mmol) and 80 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the reaction solution was filtered witha glass filter, the insoluble portion was removed, and the filtrate wasconcentrated under reduced pressure. The deposited solid wasreprecipitated with hexane at −78° C. and dried under reduced pressureto obtain 0.19 g (0.28 mmol, 28% yield) of compound A-40 as a red orangepowder.

¹H-NMR(CDCl₃): 0.80-1.80 (m,18H), 6.50-7.90 (m,14H), 8.00-8.20 (m,2H)

FD-mass spectrometry: 692 (M+)

Elemental analysis: Ti: 7.0% (6.9)

Calculated value in parentheses.

Synthesis Example 74

Synthesis of Compound B-40

After charging 0.58 g (2.02 mmol) of compound L40 and 40 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.50 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.42 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing a zirconiumtetrachloride.2THF complex (0.38 g, 1.00 mmol) and 80 ml oftetrahydrofuran that had been cooled to −78° C. After completion of thedropwise addition, stirring was continued while slowly increasing thetemperature to room temperature. After further stirring for 8 hours atroom temperature, the solvent of the reaction solution was distilledoff. The resulting solid was reslurried with 150 ml of diethyl ether,the insoluble portion was removed off with a glass filter, and then thefiltrate was concentrated under reduced pressure. The deposited solidwas reprecipitated with hexane at −78° C. and dried under reducedpressure to obtain 0.23 g (0.31 mmol, 31% yield) of compound B-40 as ayellow powder represented by the formula given below.

¹H-NMR(CDCl₃): 0.80-1.70 (m, 18H), 6.50-7.90 (m,14H), 8.20 (s,2H)

FD-mass spectrometry: 734 (M+)

Elemental analysis: Zr: 12.2% (12.4)

Calculated value in parentheses.

Synthesis Example 75

Synthesis of Compound A-41

After charging 0.50 g (1.15 mmol) of compound L41 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.47 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.3 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.15mmol) and 10 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After further stirringfor 8 hours at room temperature, the solvent of the reaction solutionwas distilled off, and the resulting solid was dissolved in 25 ml ofmethylene chloride. The insoluble portion was filtered off with a glassfilter, the filtrate was concentrated under reduced pressure, and thedeposited solid was reprecipitated with diethyl ether, methylenechloride and hexane and dried under reduced pressure to obtain 0.49 g(0.93 mmol, 76% yield) of compound A-41 as an orange powder.

FD-mass spectrometry: 525 (M+)

Elemental analysis: Ti: 8.9% (9.1)

Calculated value in parentheses.

Synthesis Example 76

Synthesis of Compound B-41

After charging 0.50 g (1.15 mmol) of compound L41 and 10 ml of diethylether into a 100 ml reactor that had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.47 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.36 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride.2THF (0.43g, 1.15 mmol) in 10 ml of tetrahydrofuran that had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. After firststirring for 8 hours at room temperature and then stirring for 12 hoursunder reflux, the solvent of the reaction solution was distilled off.The resulting solid was dissolved in 25 ml of methylene chloride, andthe insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.36 g (0.63 mmol, 51% yield) ofcompound B-41 as a yellow powder.

¹H-NMR(CDCl₃): 1.41 (s,18H), 2.10 (s,2H), 3.70 (s,2H), 6.94 (t,2H), 7.30(dd,2H), 7.50 (dd,2H), 8.39 (s,2H)

FD-mass spectrometry: 568 (M+)

Elemental analysis: Zr: 16.2% (16.0)

Calculated value in parentheses.

Synthesis Example 77

Synthesis of Compound A-42

After charging 0.500 g (1.22 mmol) of compound L42 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.45 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen slowly added dropwise to a mixed solution containing 2.45 ml of atitanium tetrachloride solution (0.5 mmol/ml heptane solution, 1.23mmol) and 10 ml of diethyl ether which had been cooled to −78° C. Aftercompletion of the dropwise addition, stirring was continued while slowlyincreasing the temperature to room temperature. After stirring for 8hours at room temperature, the solvent of the reaction solution wasdistilled off, and the resulting solid was dissolved in 25 ml ofmethylene chloride. After filtering the insoluble portion with a glassfilter, the filtrate was concentrated under reduced pressure, and thedeposited solid was reprecipitated with diethyl ether, methylenechloride and hexane and dried under reduced pressure to obtain 0.25 g(0.45 mmol, 40% yield) of compound A-42 as a red brown powder.

FD-mass spectrometry: 552 (M+)

Elemental analysis: Ti: 9.0% (8.7)

Calculated value in parentheses.

Synthesis Example 78

Synthesis of Compound B-42

After charging 0.50 g (1.22 mmol) of compound L42 and 10 ml of diethylether into a 100 ml reactor which had been adequately dried andsubstituted with argon, they were cooled to −78° C. and stirred. Afterdropwise adding 1.52 ml of n-butyllithium (1.61 mmol/ml n-hexanesolution, 2.45 mmol) over 5 minutes, the temperature was slowlyincreased to room temperature, and stirring was continued for 4 hours atroom temperature to prepare a lithium salt solution. The solution wasthen added dropwise to a solution of zirconium tetrachloride.2THF (0.46g, 1.22 mmol) in 10 ml of tetrahydrofuran that had been cooled to −78°C. After completion of the dropwise addition, stirring was continuedwhile slowly increasing the temperature to room temperature. After firststirring for 8 hours at room temperature and then stirring for 6 hoursunder reflux, the solvent of the reaction solution was distilled off.The resulting solid was dissolved in 25 ml of methylene chloride, andthe insoluble portion was removed with a glass filter. The filtrate wasconcentrated under reduced pressure, and the deposited solid wasreprecipitated with methylene chloride, diethyl ether and hexane anddried under reduced pressure to obtain 0.22 g (0.37 mmol, 32% yield) ofcompound B-42 as a yellow powder represented by the formula given below.

FD-mass spectrometry: 596 (M+)

Elemental analysis: Zr: 15.5% (15.3)

Calculated value in parentheses.

All the procedures for transition metal complex synthesis were conductedunder an argon or nitrogen atmosphere, and the solvent employed was acommercially available anhydrous solvent.

Specific examples for polymerization processes according to the presentinvention are given below.

Example 1

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with 100 l/hr of ethylene. Thereafter, 1.1875 mmol (in termsof aluminum atom) of methylaluminoxane (MAO) was added, and successively0.00475 mmol of the compound A-1 obtained in Synthesis Example 1 wasadded to initiate polymerization. The reaction was conducted at 25° C.for 30 minutes in an ethylene gas atmosphere at normal pressure, andthen a small amount of isobutanol was added to terminate thepolymerization. After the polymerization was completed, the reactionproduct was introduced into a large amount of methanol to precipitate apolymer in the whole amount. Then, hydrochloric acid was added, andfiltration was effected using a glass filter. The resulting polymer wasvacuum dried at 80° C. for 10 hours, to obtain 8.02 g of polyethylene(PE).

The polymerization activity was 3,400 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 8.44 dl/g.

Example 2

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with 100 l/hr of ethylene. Thereafter, 1.25 mmol (in terms ofaluminum atom) of methylaluminoxane and 0.005 mmol of the compound A-1were added to initiate polymerization. The polymerization was conductedat 50° C. for 10 minutes, and then a small amount of isobutanol wasadded to terminate the polymerization.

The polymer suspension obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 3.30 g of polyethylene. Thepolymerization activity was 3,960 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 6.37 dl/g.

Example 3

Polymerization was carried out in the same manner as in Example 2,except that the polymerization temperature was varied to 75° C. Theresults are set forth in Table 1.

Example 4

Polymerization was carried out in the same manner as in Example 2,except that the polymerization temperature was varied to 25° C. and 2l/hr of hydrogen was fed together with ethylene. The results are setforth in Table 1.

Example 5 TA-1, B

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with 100 l/hr of ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum (TIBA) was added, and successively 0.005 mmol of thecompound A-1 and 0.006 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate (TrB) were added toinitiate polymerization. The reaction was conducted at 25° C. for 1 hourin an ethylene gas atmosphere at normal pressure, and then a smallamount of isobutanol was added to terminate the polymerization. Afterthe polymerization was completed, the reaction product was introducedinto a large amount of methanol to precipitate a polymer in the wholeamount. Then, hydrochloric acid was added, and filtration was effectedusing a glass filter. The resulting polymer was vacuum dried at 80° C.for 10 hours, to obtain 0.50 g of polyethylene.

The polymerization activity was 100 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 10.6 dl/g.

Example 6

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with 100 l/hr of ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum, 0.005 mmol of the compound A-1 and 0.006 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate were added toinitiate polymerization. The polymerization was conducted at 75° C. for30 minutes, and then a small amount of isobutanol was added to terminatethe polymerization.

The polymer suspension obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 0.71 g of polyethylene. Thepolymerization activity was 280 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 7.22 dl/g.

Example 7

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with 100 l/hr of ethylene. Thereafter, 2.5 mmol (in terms ofaluminum atom) of methylaluminoxane was added, and successively 0.005mmol of the zirconium compound B-1 was added to initiate polymerization.The reaction was conducted at 25° C. for 5 minutes in an ethylene gasatmosphere at normal pressure, and then a small amount of isobutanol wasadded to terminate the polymerization. After the polymerization wascompleted, the reaction product was introduced into a large amount ofmethanol to precipitate a polymer in the whole amount. Then,hydrochloric acid was added, and filtration was effected using a glassfilter. The resulting polymer was vacuum dried at 80° C. for 10 hours,to obtain 6.10 g of polyethylene.

The polymerization activity was 14,600 g/mmol-Zr·hr, and the intrinsicviscosity [η] of the polyethylene was 0.30 dl/g.

Examples 8-24

Ethylene polymerization was carried out in the same manner as in Example7, except that the polymerization conditions were varied to those shownin Table 1. The results are set forth in Table 1.

Example 25

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with 100 l/hr of ethylene. Thereafter, 0.25 mmol oftriisobutylaluminum was added, and then a pre-mixed solution of 0.05mmol of triisobutylaluminum, 0.005 mmol of the compound B-1 and 0.006mmol of triphenylcarbeniumtetrakis(pentafluoro-phenyl)borate was addedto initiate polymerization. The polymerization was conducted at 25° C.for 5 minutes, and then a small amount of isobutanol was added toterminate the polymerization. The polymer solution obtained wasintroduced into 1.5 liters of methanol containing a small amount ofhydrochloric acid to precipitate a polymer. The polymer was washed withmethanol and vacuum dried at 80° C. for 10 hours, to obtain 0.99 g ofpolyethylene. The polymerization activity was 2,380 g/mmol-Zr·hr, andthe intrinsic viscosity [η] of the polyethylene was 22.4 dl/g.

Example 26

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with ethylene. Thereafter, 0.25 mmol of triisobutylaluminumwas added, and successively 0.0005 mmol of the zirconium compound B-1and 0.001 mmol of triphenylcarbeniumtetrakis(pentafluoro-phenyl)boratewere added to initiate polymerization. The reaction was conducted at 25°C. for 10 minutes in an ethylene gas atmosphere at normal pressure.After the polymerization was completed, the reaction product wasintroduced into a large amount of methanol to precipitate a polymer inthe whole amount. Then, hydrochloric acid was added, and filtration waseffected using a glass filter. The resulting polymer was vacuum dried at80° C. for 10 hours, to obtain 0.34 g of polyethylene (PE).

The polymerization activity was 4,080 g/mmol-Zr·hr, and the intrinsicviscosity [η] of the polyethylene was 12.6 dl/g.

Examples 27-31

Ethylene polymerization was carried out in the same manner as in Example26, except that the polymerization conditions were varied to those shownin Table 1. The results are set forth in Table 1. TABLE 1 Results ofethylene polymerization at normal pressure Amount Amount Temp. TimeYield Activity [η] Ex. Compound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 1 A-1 0.00475 MAO 1.1875 25 30 8.02 3400 8.442 A-1 0.005 MAO 1.25 50 10 3.30 3960 6.37 3 A-1 0.005 MAO 1.25 75 103.14 3770 5.48 4 A-1 0.005 MAO 1.25 25 10 3.23 3880 3.53 5 A-1 0.005TrB/TIBA 0.006/0.25 25 60 0.50 100 10.6 6 A-1 0.005 TrB/TIBA 0.006/0.2575 30 0.71 280 7.22 7 B-1 0.005 MAO 2.5 25 5 6.10 14600 0.30 8 B-10.0005 MAO 0.5 25 5 4.85 116000 0.31 9 B-1 0.0002 MAO 1.25 25 5 3.29197000 0.32 10 B-1 0.0001 MAO 0.5 25 5 2.72 326000 0.21 11 B-1 0.00002MAO 1.25 25 5 0.77 462000 0.28 12 B-1 0.00002 MAO 1.25 40 5 0.90 5400000.33 13 B-1 0.0002 MAO 1.25 0 5 3.09 185000 0.27 14 B-1 0.0002 MAO 1.2510 5 3.64 218000 0.29 15 B-1 0.0002 MAO 1.25 30 5 3.70 222000 0.26 16B-1 0.0002 MAO 1.25 40 5 4.21 253000 0.33 17 B-1 0.0002 MAO 1.25 50 52.95 177000 0.30 18 B-1 0.0002 MAO 1.25 60 5 2.99 179000 0.39 19 B-10.0002 MAO 1.25 70 5 2.11 127000 0.41 20 B-1 0.00008 MAO 1.25 25 5 2.67401000 0.28 21 B-1 0.00008 MAO 1.25 25 15 7.58 379000 0.30 22 B-10.00008 MAO 1.25 25 30 12.42 311000 0.31 23 B-1 0.0002 MAO 1.25 50 155.89 118000 0.60 24 B-1 0.0002 MAO 1.25 50 30 9.67 96700 1.23 25 B-10.005 TrB/TIBA 0.006/0.30 25 5 0.99 2380 22.40 26 B-1 0.0005 TrB/TIBA0.001/0.25 25 10 0.34 4080 12.6 27 B-1 0.001 TrB/TIBA 0.002/0.25 25 100.31 1860 15.0 28 B-1 0.0025 TrB/TIBA 0.005/0.25 25 10 1.28 3070 14.8 29B-1 0.0005 TrB/TIBA 0.001/0.25 25 10 0.27 3240 20.1 30 B-1 0.0005TrB/TIBA 0.001/0.25 50 10 0.22 2640 21.1 31 B-1 0.0005 TrB/TIBA0.001/0.25 75 10 0.12 1440 16.3MAO: MethylaluminoxaneTIBA: TriisobutylaluminumTrB: Triphenylcarbeniumtetrakis(pentafluoro-phenyl)borate

Examples 32-36

Ethylene polymerization was carried out in the same manner as in Example7, except that the compounds shown in Table 2 were used and thepolymerization conditions were varied to those shown in Table 2. Theresults are set forth in Table 2. TABLE 2 Results of ethylenepolymerization at normal pressure Amount Amount Temp. Time YieldActivity [η] Ex. Compound (mmol) Cocatalyst (mmol) (° C.) (min) (g)(g/mmol-M · h) (dl/g) 32 C-1 0.005 MAO 1.25 25 5 2.69 6460 0.75 33 C-10.005 MAO 1.25 75 5 3.47 8330 0.47 34 D-1 0.005 MAO 1.25 25 30 0.03 128.32 35 E-1 0.005 MAO 1.25 25 30 0.02 8 2.51 36 F-1 0.005 MAO 1.25 25 300.01 4 1.05

Examples 37-52

In the case where methylaluminoxane was used as a cocatalyst, ethylenepolymerization was carried out in the same manner as in Example 7,except that the compounds shown in Table 3 were used and thepolymerization conditions were varied to those shown in Table 3. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 3 were usedand the polymerization conditions were varied to those shown in Table 3.The results are set forth in Table 3. TABLE 3 Amount Amount Temp. TimeYield Activity [η] EX. Compound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 37 B-2 0.005 MAO 1.25 25 30 0.69 270 8.32 38B-3 0.005 MAO 1.25 25 30 2.15 860 0.4 39 A-6 0.005 MAO 1.25 25 5 0.541300 4.31 40 A-6 0.005 MAO 1.25 75 5 0.76 1820 4.31 41 B-6 0.0005 MAO1.25 25 5 1.38 33100 0.24 42 A-7 0.005 MAO 1.25 25 5 1.93 4630 6.84 43A-7 0.005 MAO 1.25 75 5 1.48 3550 5.34 44 B-7 0.005 MAO 1.25 25 5 1.724130 0.10 45 A-8 0.005 MAO 1.25 25 30 0.90 360 5.70 46 A-8 0.005TrB/TIBA 0.006/0.25 25 30 1.03 410 4.70 47 B-8 0.0001 MAO 0.5 25 5 1.01121000 0.21 48 B-8 0.005 TrB/TIBA 0.006/0.25 25 30 2.57 1030 14.2 49 A-90.005 TrB/TIBA 0.006/0.25 25 30 0.25 100 11.7 50 B-9 0.0001 MAO 0.5 25 50.27 32400 0.24 51 B-9 0.005 TrB/TIBA 0.006/0.25 25 5 2.87 6890 0.30 52A-10 0.005 MAO 1.25 25 60 0.48 96 11.0

Examples 53-78

In the case where methylaluminoxane was used as a cocatalyst, ethylenepolymerization was carried out in the same manner as in Example 7,except that the compounds shown in Table 4 were used and thepolymerization conditions were varied to those shown in Table 4. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 4 were usedand the polymerization conditions were varied to those shown in Table 4.The results are set forth in Table 4. TABLE 4 Amount Amount Temp. TimeYield Activity [η] EX. Compound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 53 A-11 0.005 MAO 1.25 25 5 2.57 6160 3.71 54A-11 0.005 TrB/TIBA 0.006/0.25 25 30 0.95 380 7.22 55 B-11 0.0005 MAO1.25 25 5 3.34 80000 0.42 56 B-11 0.005 TrB/TIBA 0.006/0.25 25 5 2.596220 0.48 57 A-12 0.005 MAO 1.25 25 5 3.28 7870 4.40 58 A-12 0.005TrB/TIBA 0.006/0.25 25 30 1.81 724 10.0 59 B-12 0.0001 MAO 1.25 25 53.71 445200 0.45 60 B-12 0.005 TrB/TIBA 0.006/0.25 25 5 4.63 11100 0.4661 A-13 0.005 MAO 1.25 25 5 1.13 2710 3.54 62 A-13 0.005 TrB/TIBA0.006/0.25 25 30 0.92 370 5.57 63 B-13 0.0001 MAO 1.25 25 5 2.78 3336000.22 64 B-13 0.005 TrB/TIBA 0.006/0.25 25 10 3.30 3960 10.7 65 A-140.005 MAO 1.25 25 5 1.93 4640 4.86 66 A-14 0.005 TrB/TIBA 0.006/0.25 2530 0.29 120 7.63 67 B-14 0.0001 MAO 1.25 25 5 2.02 242400 0.31 68 B-140.005 TrB/TIBA 0.006/0.25 25 5 1.83 4390 0.69 69 A-15 0.005 MAO 1.25 2510 2.05 2460 4.90 70 B-15 0.005 MAO 1.25 25 10 3.22 3870 0.74 71 A-160.005 MAO 1.25 25 30 0.71 280 3.47 72 B-16 0.005 MAO 1.25 25 10 0.41 4900.58 73 A-17 0.005 MAO 1.25 25 30 1.52 608 5.50 74 B-17 0.005 MAO 1.2525 30 2.16 860 0.40 75 A-18 0.005 MAO 1.25 25 30 0.34 136 3.98 76 B-180.0005 MAO 1.25 25 5 1.68 40300 4.42 77 B-18 0.005 TrB/TIBA 0.006/0.2525 5 2.22 5330 1.87 78 B-19 0.005 TrB/TIBA 0.006/0.25 25 30 0.50 20024.40

Examples 79-111

In the case where methylaluminoxane was used as a cocatalyst, ethylenepolymerization was carried out in the same manner as in Example 7,except that the compounds shown in Table 5 were used and thepolymerization conditions were varied to those shown in Table 5. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 5 were usedand the polymerization conditions were varied to those shown in Table 5.The results are set forth in Table 5. TABLE 5 Amount Amount Temp. TimeYield Activity [η] EX. Compound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 79 A-21 0.005 MAO 1.25 25 5 3.22 7730 6.34 80A-21 0.005 TrB/TIBA 0.006/0.25 25 30 0.57 230 9.06 81 B-21 0.0001 MAO1.25 25 5 1.24 148800 0.27 82 B-21 0.005 TrB/TIBA 0.006/0.25 25 5 1.182830 3.06 83 A-22 0.005 MAO 1.25 25 5 1.78 4270 4.00 84 B-22 0.0002 MAO1.25 25 5 1.60 96000 0.41 85 B-22 0.005 TrB/TIBA 0.006/0.25 25 5 4.6411100 0.24 86 A-23 0.005 MAO 1.25 25 10 0.38 460 1.53 87 B-23 0.005 MAO1.25 25 30 2.34 940 0.31 88 A-24 0.005 TrB/TIBA 0.006/0.25 25 30 0.44176 7.11 89 B-24 0.005 MAO 1.25 25 15 1.62 1300 2.03 90 B-24 0.005TrB/TIBA 0.006/0.25 25 30 1.10 440 0.57 91 A-25 0.005 MAO 1.25 25 5 1.714100 6.55 92 A-25 0.005 TrB/TIBA 0.006/0.25 25 15 1.30 1040 10.5 93 B-250.0002 MAO 1.25 25 5 1.89 113000 0.44 94 B-25 0.005 TrB/TIBA 0.006/0.2525 5 4.34 10400 0.44 95 A-26 0.005 MAO 1.25 25 5 1.04 2450 3.44 96 B-260.0001 MAO 61.25 25 5 2.62 314000 0.43 97 B-26 0.005 TrB/TIBA 0.006/0.2525 5 0.95 2300 12.5 98 A-27 0.005 MAO 1.25 25 15 0.31 240 1.81 99 B-270.005 MAO 1.25 25 5 5.11 12300 6.34 100 B-27 5E−05 MAO 0.25 25 5 2.4157800 10.6 101 B-27 2E−05 MAO 0.25 25 5 1.31 78400 7.73 102 B-27 0.005TrB/TIBA 0.006/0.25 25 5 1.98 4750 5.67 103 A-28 0.005 MAO 1.25 25 51.35 3240 4.92 104 A-28 0.005 TrB/TIBA 0.006/0.25 25 30 0.34 140 12.4105 B-28 0.0001 MAO 1.25 25 5 2.03 244000 0.76 106 B-28 0.005 TrB/TIBA0.006/0.25 25 10 4.20 5040 19.6 107 A-29 0.005 TrB/TIBA 0.006/0.25 25 300.18 72 13.2 108 B-29 0.005 MAO 1.25 25 30 0.49 200 8.43 109 A-30 0.005TrB/TIBA 0.006/0.25 25 30 0.16 60 19.7 110 B-30 0.005 MAO 1.25 25 300.30 120 12.0 111 B-30 0.005 TrB/TIBA 0.006/0.25 25 30 0.45 180 23.0

Examples 112-121

In the case where methylaluminoxane was used as a cocatalyst, ethylenepolymerization was carried out in the same manner as in Example 7,except that the compounds shown in Table 6 were used and thepolymerization conditions were varied to those shown in Table 6. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 6 were usedand the polymerization conditions were varied to those shown in Table 6.

The results are set forth in Table 6. TABLE 6 Amount Amount Temp. TimeYield Activity [η] EX. Compound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 112 A-31 0.005 MAO 1.25 25 30 0.63 250 5.49113 A-31 0.005 TrB/TIBA 0.006/0.25 25 30 0.49 200 15.30 114 B-31 0.005MAO 1.25 25 30 1.38 550 0.99 115 A-32 0.005 MAO 1.25 25 60 0.02 2 8.81116 A-35 0.005 MAO 1.25 25 60 0.01 4 9.09 117 A-39 0.005 MAO 1.25 25 300.10 40 1.66 118 B-39 0.005 MAO 1.25 25 5 1.06 2540 0.29 119 B-39 0.005TrB/TIBA 0.006/0.25 25 20 1.10 660 4.42 120 A-40 0.005 MAO 1.25 25 301.10 440 4.59 121 B-40 0.005 MAO 1.25 25 30 0.25 200 1.28

Examples 122-130

In the case where methylaluminoxane was used as a cocatalyst, ethylenepolymerization was carried out in the same manner as in Example 7,except that the compounds shown in Table 7 were used and thepolymerization conditions were varied to those shown in Table 7. In thecase where triisobutylaluminum andtriphenylcarbeniumtetrakis(pentafluorophenyl)borate were used ascocatalysts, ethylene polymerization was carried out in the same manneras in Example 26, except that the compounds shown in Table 7 were usedand the polymerization conditions were varied to those shown in Table 7.

The results are set forth in Table 7. TABLE 7 Amount Amount Temp. TimeYield Activity [η] EX. Compound (mmol) Cocatalyst (mmol) (° C.) (min)(g) (g/mmol-M · h) (dl/g) 122 A-34 0.005 MAO 1.25 25 60 0.01 2 6.31 123A-35 0.005 MAO 1.25 25 60 0.05 10 5.88 124 A-36 0.005 MAO 1.25 25 600.03 6 7.77 125 B-37 0.005 MAO 1.25 25 60 0.01 2 6.09 126 B-38 0.005 MAO12.5 25 60 0.01 2 8.03 127 A-41 0.005 MAO 1.25 25 15 0.96 770 4.00 128B-41 0.005 TrB/TIBA 0.006/0.25 25 5 0.59 1420 7.07 129 A-43 0.005TrB/TIBA 0.006/0.25 25 15 0.18 140 6.81 130 B-43 0.005 TrB/TIBA0.006/0.25 25 15 1.35 1080 0.84

Example 131

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with a mixed gas of 50 l/hr of ethylene and 150 l/hr ofpropylene. Thereafter, 1.25 mmol (in terms of aluminum atom) ofmethylaluminoxane and 0.005 mmol of the compound A-1 were added toinitiate polymerization. The polymerization was conducted at 25° C. for15 minutes, and then a small amount of isobutanol was added to terminatethe polymerization.

The polymer suspension obtained was introduced into 1.5 liters ofmethanol containing a small amount of hydrochloric acid to precipitate apolymer. Then, filtration was effected using a glass filter to removethe solvent. The resulting polymer was washed with methanol and vacuumdried at 80° C. for 10 hours, to obtain 0.95 g of an ethylene/propylenecopolymer. The polymerization activity was 760 g/mmol-Ti·hr, thepropylene content as measured by IR was 4.67% by mol, and the intrinsicviscosity [η] of the copolymer was 2.21 dl/g.

Example 132

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced, and the liquid phase and the gas phase weresaturated with a mixed gas of 100 l/hr of ethylene and 100 l/hr ofpropylene. Thereafter, 0.25 mmol of triisobutylaluminum was added, andthen a pre-mixed solution of 0.025 mmol of triisobutylaluminum, 0.0025mmol of the compound B-1 and 0.005 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate (TrB) was added toinitiate polymerization. The polymerization was conducted at 50° C. for5 minutes, and then a small amount of isobutanol was added to terminatethe polymerization.

The polymer solution obtained was introduced into 1.5 liters of methanolcontaining a small amount of hydrochloric acid to precipitate a polymer.The polymer was washed with methanol and vacuum dried at 130° C. for 10hours, to obtain 1.63 g of an ethylene/propylene copolymer. Thepolymerization activity was 7,820 g/mmol-Zr·hr, the propylene content asmeasured by IR was 20.7% by mol, and the intrinsic viscosity [η] of thecopolymer was 13.4 dl/g.

Example 133

Copolymerization was carried out in the same manner as in Example 132,except that the compound B-1 was used, the flow rates of ethylene andpropylene were varied to 50 l/hr and 150 l/hr, respectively, and thepolymerization temperature and the amounts of the catalysts were variedto those shown in Table 8.

The results are set forth in Table 8.

Examples 134-149

Copolymerization was carried out in the same manner as in Example 131,except that the compounds shown in Table 8 were used.

The results are set forth in Table 8. TABLE 8 Results ofethylene/propylene copolymerization at normal pressure Propylene AmountAmount Temp. Time Yield Activity [η] content Ex. Compound (mmol)Cocatalyst (mmol) (° C.) (min) (g) (g/mmol-M · h) (dl/g) (mol %) 131 A-10.005 MAO 1.25 25 15 0.95 760 2.21 4.67 132 B-1 0.0025 TrB/TIBA0.005/0.275 50 5 1.63 7820 13.40 20.7 133 B-1 0.005 TrB/TIBA 0.006/0.325 10 1.28 1540 12.40 31.3 134 B-1 0.005 MAO 1.25 25 10 8.42 10100 0.0329.2 135 C-1 0.005 MAO 1.25 25 10 2.30 2760 0.32 7.19 136 B-6 0.005 MAO1.25 25 10 3.64 4370 0.14 10.2 137 B-8 0.005 MAO 1.25 25 10 4.15 49800.13 12.43 138 B-9 0.005 MAO 1.25 25 10 3.31 3970 0.13 8.3 139 A-110.005 MAO 1.25 25 10 0.69 830 0.80 7.8 140 A-12 0.005 MAO 1.25 25 100.37 400 0.41 3.8 141 B-12 0.005 MAO 1.25 25 10 4.14 4970 0.11 18.5 142B-13 0.005 MAO 1.25 25 10 7.86 9430 0.05 30.1 143 B-18 0.005 MAO 1.25 2510 1.92 2300 3.63 3.09 144 A-21 0.005 MAO 1.25 25 10 0.74 890 1.92 8.2145 A-22 0.005 MAO 1.25 25 10 6.85 8220 0.08 15.4 146 B-25 0.005 MAO1.25 25 10 3.86 4630 0.16 12.1 147 B-26 0.005 MAO 1.25 25 10 4.28 51400.05 26.3 148 B-27 0.005 MAO 1.25 25 10 3.55 4250 1.11 6.5 149 B-280.005 MAO 1.25 25 10 4.51 5410 0.19 14.5

Example 150

To a 500 ml glass autoclave thoroughly purged with nitrogen, 250 ml oftoluene was introduced. Then, 100 l/hr of ethylene and 20 l/hr ofbutadiene were passed through the system. After 10 minutes, 5.0 mmol (interms of aluminum atom) of methylaluminoxane was added, and successively0.01 mmol of the titanium compound A-1 was added to initiatepolymerization. The reaction was conducted at 25° C. for 20 minutes withpassing the mixed gas of ethylene and butadiene at normal pressure, andthen a small amount of methanol was added to terminate thepolymerization. The reaction product was introduced into a large amountof hydrochloric acid/methanol to precipitate a polymer in the wholeamount. The polymer was filtered with a glass filter and vacuum dried at80° C. for 10 hours, to obtain 0.53 g of an ethylene/butadienecopolymer.

The polymerization activity per 1 mmol of titanium was 149 g, and theintrinsic viscosity [η] of the copolymer was 1.46 dl/g. The content ofall the butadiene units in the copolymer, as determined by NMR analysis,was 0.9% by mol (1,4-cis form+1,4-trans form: 0.8% by mol, 1,2-vinylform: 0.1% by mol, cyclopentane skeleton: less than 0.1% by mol (lowerthan the detection limit)).

Example 151

Polymerization was carried out in the same manner as in Example 150,except that a zirconium compound B-1 was used in place of the titaniumcompound A-1. The yield of the copolymer was 2.65 g.

The polymerization activity per 1 mmol of zirconium was 3,180 g, and theintrinsic viscosity [η] of the copolymer was 0.70 dl/g. The content ofall the butadiene units in the copolymer, as determined by NMR analysis,was 1.2% by mol (1,4-cis form+1,4-trans form: 1.1% by mol, 1,2-vinylform: 0.1% by mol, cyclopentane skeleton: less than 0.1% by mol (lowerthan the detection limit)).

Example 152

Polymerization was carried out in the same manner as in Example 151,except that the polymerization time was varied to 20 minutes and theflow rates of ethylene and butadiene were varied to 20 l/hr and 80 l/hr,respectively. The yield of the copolymer was 0.74 g.

The polymerization activity per 1 mmol of zirconium was 446 g, and theintrinsic viscosity [η] of the copolymer was 0.87 dl/g. The content ofall the butadiene units in the copolymer, as determined by NMR analysis,was 5.3% by mol (1,4-cis form+1,4-trans form: 4.7% by mol, 1,2-vinylform: 0.6% by mol, cyclopentane skeleton: less than 0.1% by mol (lowerthan the detection limit)).

Example 153

Polymerization was carried out in the same manner as in Example 151,except that the polymerization time was varied to 5 minutes and the flowrates of ethylene and butadiene were varied to 50 l/hr and 50 l/hr,respectively. The yield of the copolymer was 0.57 g.

The polymerization activity per 1 mmol of zirconium was 342 g, and theintrinsic viscosity [η] of the copolymer was 0.34 dl/g. The content ofall the butadiene units in the copolymer, as determined by NMR analysis,was 2.4% by mol (1,4-cis form+1,4-trans form: 2.3% by mol, 1,2-vinylform: 0.1% by mol, cyclopentane skeleton: less than 0.1% by mol (lowerthan the detection limit)).

Example 154

Polymerization was carried out in the same manner as in Example 153,except that the polymerization temperature was varied to 50° C. Theyield of the copolymer was 0.627 g.

The polymerization activity was 1,488 g/mmol-Zr·hr, and the intrinsicviscosity [η] of the copolymer was 0.16 dl/g. The content of thebutadiene units in the copolymer, as determined by NMR analysis, was3.3% by mol (1,4-cis form+1,4-trans form: 3.2% by mol, 1,2-vinyl form:0.1% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)).

Example 155

Polymerization was carried out in the same manner as in Example 153,except that the polymerization temperature was varied to 50° C. and theflow rates of ethylene and butadiene were varied to 40 l/hr and 60 l/hr,respectively. The yield of the copolymer was 0.37 g.

The polymerization activity was 888 g/mmol-Zr·hr, and the intrinsicviscosity [η] of the copolymer was 0.17 dl/g. The content of thebutadiene units in the copolymer, as determined by NMR analysis, was4.8% by mol (1,4-cis form+1,4-trans form: 4.6% by mol, 1,2-vinyl form:0.2% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)).

Example 156

Polymerization was carried out in the same manner as in Example 153,except that the polymerization temperature was varied to 60° C. and theflow rates of ethylene and butadiene were varied to 40 l/hr and 60 l/hr,respectively. The yield of the copolymer was 0.417 g.

The polymerization activity was 984 g/mmol-Zr·hr, and the intrinsicviscosity [η] of the copolymer was 0.12 dl/g. The content of thebutadiene units in the copolymer, as determined by NMR analysis, was5.8% by mol (1,4-cis form+1,4-trans form: 5.6% by mol, 1,2-vinyl form:0.2% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)). The molecular weight distribution (Mw/Mn) asmeasured by the GPC was 1.85.

Example 157

Polymerization was carried out in the same manner as in Example 153,except that the polymerization temperature was varied to 50° C. and theflow rates of ethylene and butadiene were varied to 30 l/hr and 70 l/hr,respectively. The yield of the copolymer was 0.24 g.

The polymerization activity was 576 g/mmol-Zr·hr, and the intrinsicviscosity [η] of the copolymer was 0.14 dl/g. The content of thebutadiene units in the copolymer, as determined by NMR analysis, was6.6% by mol (1,4-cis form+1,4-trans form: 6.3% by mol, 1,2-vinyl form:0.2% by mol, cyclopentane skeleton: less than 0.1% by mol (lower thanthe detection limit)). The molecular weight distribution (Mw/Mn) asmeasured by the GPC was 2.05.

Example 158

To a 1-liter SUS autoclave thoroughly purged with nitrogen, 500 ml ofheptane was introduced, and the gas phase and the liquid were saturatedwith ethylene at 50° C. Then, 1.25 mmol (in terms of aluminum) ofmethylaluminoxane and 0.001 mmol of the compound A-1 were added, andpolymerization was performed for 15 minutes under an ethylene pressureof 8 kg/cm²-G.

To the polymer suspension obtained, 1.5 liters of methanol containing asmall amount of hydrochloric acid was added to precipitate a polymer.Then, filtration was effected using a glass filter to remove thesolvent. The resulting polymer was washed with methanol and vacuum driedat 80° C. for 10 hours, to obtain 11.22 g of polyethylene. Thepolymerization activity was 44.9 g/mmol-Ti·hr, and the intrinsicviscosity [η] of the polyethylene was 7.91 dl/g.

Examples 159-162

Polymerization was carried out in the same manner as in Example 158,except that the compounds shown in Table 9 were used and thepolymerization conditions were varied to those shown in Table 9.

The results are set forth in Table 9. TABLE 9 Examples of ethylenepolymerization under pressure Amount Amount Temp. Time Yield Activity[η] Ex. Compound (mmol) Cocatalyst (mmol) (° C.) (min) (g) (g/mmol-M ·h) (dl/g) 158 A-1 0.001 MAO 1.25 50 15 11.22 44.9 7.91 159 A-1 0.001 MAO1.25 75 15 11.96 47.8 7.31 160 B-1 0.00005 MAO 1.25 50 15 14.90 11921.15 161 C-1 0.00025 MAO 1.25 50 15 8.28 132 2.30 162 A-7 0.001 MAO 1.2550 15 4.83 19.3 4.44

Example 163

Preparation of Solid Catalyst Component

In 154 liters of toluene, 10 kg of silica having been dried at 250° C.for 10 hours was suspended, and the suspension was cooled to 0° C. Then,57.5 liters of a methylaluminoxane solution (Al=1.33 mol/l) was dropwiseadded over a period of 1 hour. During the addition, the temperature ofthe system was maintained at 0° C., and the reaction was conducted at 0°C. for 30 minutes. Then, the temperature of the system was raised up to95° C. over a period of 1.5 hours, and at this temperature the reactionwas conducted for 20 hours. The temperature of the system was thenlowered to 60° C., and the supernatant liquid was removed bydecantation. The resulting solid catalyst component was washed twicewith toluene and resuspended in toluene, to obtain a solid catalystcomponent (A) (whole volume: 200 liters).

22.4 Milliliters of the suspension of the solid catalyst component (A)as obtained above was transferred into a 200 ml glass flask, and then175 ml of toluene and 4.8 ml of a toluene solution of the compound A-1(Ti=0.01 mmol/l) were added. The mixture was stirred at room temperaturefor 2 hours. The resulting suspension was washed three times with 200 mlof hexane, and hexane was added to give 200 ml of a suspension and asolid catalyst component (B).

Polymerization

To a 2-liter SUS autoclave thoroughly purged with nitrogen, 1 liter ofheptane was introduced, and the gas phase and the liquid were saturatedwith ethylene at 50° C. Then, 1.0 mmol of triisobutylaluminum and 0.005mmol (in terms of Ti atom) of the solid catalyst component (B) wereadded, and polymerization was performed for 90 minutes under an ethylenepressure of 8 kg/cm²-G.

The polymer suspension obtained was filtered with a glass filter, washedtwice with 500 ml of hexane and vacuum dried at 80° C. for 10 hours, toobtain 8.96 g of polyethylene. The polymerization activity was 1,790g/mmol-Ti·hr, and the intrinsic viscosity [η] of the polyethylene was11.7 dl/g.

Example 164

To a 200 ml reactor thoroughly purged with nitrogen, 60 ml of heptaneand 40 ml of 1-hexene were introduced, and they were stirred at 25° C.Thereafter, 0.25 mmol of triisobutylaluminum was added, and then a mixedsolution of 0.1 mmol of triisobutylaluminum, 0.01 mmol of the compoundA-1 and 0.012 mmol oftriphenylcarbeniumtetrakis(penta-fluorophenyl)borate was added toinitiate polymerization. The reaction was conducted at 25° C. for 1hour, and then a small amount of isobutanol was added to terminate thepolymerization.

The polymer suspension obtained was added little by little to 1 liter ofacetone to precipitate a polymer. The polymer was separated from thesolvent and vacuum dried at 130° C. for 10 hours, to obtain 3.15 g ofpolyhexene. The polymerization activity was 315 g/mmol-Ti·hr. Themolecular weight (Mw), as measured by GPC, was 1,460,000 (in terms ofpolystyrene), and the molecular weight distribution (Mw/Mn) was 2.06.

Example 165

To a 500 ml reactor thoroughly purged with nitrogen, 250 ml of toluenewas introduced, and the liquid phase and the gas phase were saturatedwith ethylene at 25° C. Thereafter, while passing 80 l/hr of butadiene,1.0 mmol of triisobutylaluminum was added, and successively 0.01 mmol ofthe titanium compound A-1 and 0.02 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate were added toinitiate polymerization. The reaction was conducted at 25° C. for 20minutes, and then a small amount of isobutanol was added to terminatethe polymerization. After the polymerization was completed, the reactionproduct was introduced into a large amount of methanol to precipitate apolymer in the whole amount. Then, hydrochloric acid was added, andfiltration was effected using a glass filter. The resulting polymer wasvacuum dried at 80° C. for 10 hours, to obtain 1.481 g of polybutadiene.

The polymerization activity was 444 g/mmol-Ti·hr, and the molecularweight (Mw) of the copolymer was 1,760,000 (in terms of polystyrene).

1. A process for olefin polymerization, comprising: polymerizing orcopolymerizing an olefin in the presence of an olefin polymerizationcatalyst, the olefin polymerization catalyst comprising: (A) atransition metal compound represented by the following formula (I), and(B) at least one compound selected from the group consisting of: (B-1)an organometallic compound, (B-2) an organoaluminum oxy-compound, and(B-3) a compound which reacts with the transition metal compound (A) toform an ion pair:

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table, m is an integer of 1 to 6, R¹ to R⁶ may be the same ordifferent, and are each a hydrogen atom, a halogen atom, a hydrocarbongroup, a heterocyclic compound residue, an oxygen-containing group, anitrogen-containing group, a boron-containing group, a sulfur-containinggroup, a phosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring, when m is 2 or greater,two of the groups R¹ to R⁶ may be bonded to each other, with the provisothat the groups R¹ are not bonded to each other, n is a numbersatisfying a valence of M, and X is a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring. 2.The process of claim 1, wherein R⁶ in the formula (I) is a halogen atom,a hydrocarbon group, a heterocyclic compound residue, anoxygen-containing group, a nitrogen-containing group, a boron-containinggroup, a sulfur-containing group, a phosphorus-containing group, asilicon-containing group, a germanium-containing group or atin-containing group.
 3. The process of claim 1, wherein the transitionmetal compound represented by the formula (I) is a transition metalcompound represented by the following formula (I-a):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table, m is an integer of 1 to 3, R¹ to R⁶ may be the same ordifferent, and are each a hydrogen atom, a halogen atom, a hydrocarbongroup, a heterocyclic compound residue, a hydrocarbon-substituted silylgroup, a hydrocarbon-substituted siloxy group, an alkoxy group, analkylthio group, an aryloxy group, an arylthio group, an acyl group, anester group, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group, a carboxyl group, a sulfo group, a mercapto groupor a hydroxyl group, and two or more of them may be bonded to each otherto form a ring, when m is 2 or greater, two of the groups R¹ to R⁶ maybe bonded to each other, with the proviso that the groups R¹ are notbonded to each other, n is a number satisfying a valence of M, and X isa hydrogen atom, a halogen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring. 4.The process of claim 3, wherein R⁶ in the formula (I-a) is a halogenatom, a hydrocarbon group, a heterocyclic compound residue, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, a arylthiogroup, an acyl group, an ester group, a thioester group, an amido group,an imido group, an amino group, an imino group, a sulfonester group, asulfonamido group, a cyano group, a nitro group, a carboxyl group, asulfo group, a mercapto group or a hydroxyl group.
 5. The process ofclaim 1, wherein the transition metal compound represented by theformula (I) is a transition metal compound represented by the followingformula (I-a-1):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table, m is an integer of 1 to 3, R¹ to R⁶ may be the same ordifferent, and are each a hydrogen atom, a halogen atom, a hydrocarbongroup, a heterocyclic compound residue, a hydrocarbon-substituted silylgroup, a hydrocarbon-substituted siloxy group, an alkoxy group, analkylthio group, an aryloxy group, an arylthio group, an acyl group, anester group, a thioester group, an amido group, an imido group, an aminogroup, an imino group, a sulfonester group, a sulfonamido group, a cyanogroup, a nitro group or a hydroxyl group, and two or more of them may bebonded to each other to form a ring, when m is 2 or greater, two of thegroups R¹ to R⁶ may be bonded to each other, with the proviso that thegroups R¹ are not bonded to each other, n is a member satisfying avalence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbongroup of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to20 carbon atoms, an oxygen-containing group, a sulfur-containing groupor a silicon-containing group, and when n is 2 or greater, plural groupsX may be the same or different and may be bonded to each other to form aring.
 6. The process of claim 5, wherein R⁶ in the formula (I-a-1) is ahalogen atom, a hydrocarbon group, a heterocyclic compound residue, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an acyl group, an ester group, a thioester group, anamido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group ora hydroxyl group.
 7. The process of claim 1, wherein the transitionmetal compound represented by the formula (I) is a transition metalcompound represented by the following formula (I-b):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table, m is an integer of 1 to 6, R¹ to R⁶ may be the same ordifferent, and are each a hydrogen atom, a halogen atom, a hydrocarbongroup, a hydrocarbon-substituted silyl group, an alkoxy group, anaryloxy group, an ester group, an amido group, an amino group, asulfonamido group, a cyano group or a nitro group, and two or more ofthem may be bonded to each other to form a ring, and when m is 2 orgreater, two of the groups R¹ to R⁶ may be bonded to each other, withthe proviso that the groups R¹ are not bonded to each other.
 8. Theprocess of claim 5, wherein R⁶ in the formula (I-b) is a halogen atom, ahydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxygroup, an aryloxy group, an ester group, an amido group, an amino group,a sulfonamido group, a cyano group or a nitro group.
 9. The process ofclaim 1, wherein M in the transition metal compound (A) is at least onetransition metal atom selected from Groups 3 to 5 or Group 9 of theperiodic table.
 10. The process of claim 1, wherein the catalyst furthercomprises a carrier (C).
 11. A process for olefin polymerization,comprising: polymerizing or copolymerizing an olefin in the presence ofan olefin polymerization catalyst, the olefin polymerization catalystcomprising: (A′) a transition metal compound represented by thefollowing formula (II), and (B) at least one compound selected from thegroup consisting of: (B-1) an organometallic compound, (B-2) anorganoaluminum oxy-compound, and (B-3) a compound which reacts with thetransition metal compound (A′) to form an ion pair:

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table, R¹ to R¹⁰ may be the same or different, and are each ahydrogen atom, a halogen atom, a hydrocarbon group, a heterocycliccompound residue, an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, and two or more ofthem may be bonded to each other to form a ring, n is a numbersatisfying a valence of M, X is a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring,and Y is a divalent bonding group containing at least one elementselected from the group consisting of oxygen, sulfur, carbon, nitrogen,phosphorus, silicon, selenium, tin and boron, and when it is ahydrocarbon group, the hydrocarbon group has 3 or more carbon atoms. 12.The process of claim 11, wherein at least one of R⁶ and R¹⁰ in theformula (II) is a halogen atom, a hydrocarbon group, a heterocycliccompound residue, an oxygen-containing group, a nitrogen-containinggroup, a boron-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group.
 13. The process ofclaim 11, wherein the transition metal compound represented by theformula (II) is a transition metal compound represented by the followingformula (II-a):

wherein M is a transition metal atom of Group 3 to Group 11 of theperiodic table, R¹ to R¹⁰ may be the same or different, and are each ahydrogen atom, a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group,an ester group, an amido group, an amino group, a sulfonamido group, acyano group or a nitro group, and two or more of them may be bonded toeach other to form a ring, n is a number satisfying a valence of M, X isa hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group or asilicon-containing group, and when n is 2 or greater, plural groups maybe the same or different and may be bonded to each other to form a ring,and Y is a divalent bonding group containing at least one elementselected from the group consisting of oxygen, sulfur, carbon, nitrogen,phosphorus, silicon, selenium, tin and boron, and when it is ahydrocarbon group, the hydrocarbon group has 3 or more carbon atoms. 14.The process of claim 13, wherein at least one of R⁶ and R¹⁰ in theformula (II-a) is a halogen atom, a hydrocarbon group, ahydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group,an ester group, an amido group, an amino group, a sulfonamido group, acyano group or a nitro group.
 15. The process of claim 11, wherein M inthe transition metal compound (A′) is a transition metal atom of Group 4or Group 5 of the periodic table.
 16. The process of claim 11, whereinthe catalyst further comprises a carrier (C).
 17. A process for olefinpolymerization, comprising: polymerizing or copolymerizing an olefin inthe presence of an olefin polymerization catalyst, the olefinpolymerization catalyst comprising: (A″) a transition metal compoundrepresented by the following formula (III):

wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table, m is an integer of 1 to 3, R¹ is a hydrocarbon group, ahydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxygroup, an alkoxy group, an alkylthio group, an aryloxy group, anarylthio group, an ester group, a thioester group, a sulfonester groupor a hydroxyl group, R² to R⁵ may be the same or different, and are eacha hydrogen atom, a halogen atom, a hydrocarbon group, a heterocycliccompound residue, a hydrocarbon-substituted silyl group, ahydrocarbon-substituted siloxy group, an alkoxy group, an alkylthiogroup, an aryloxy group, an arylthio group, an ester group, a thioestergroup, an amido group, an imido group, an amino group, an imino group, asulfonester group, a sulfonamido group, a cyano group, a nitro group, acarboxyl group, a sulfo group, a mercapto group or a hydroxyl group, R⁶is a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silylgroup, a hydrocarbon-substituted siloxy group, an alkoxy group, analkylthio group, an aryloxy group, an arylthio group, an ester group, athioester group, an amido group, an imido group, an imino group, asulfonester group, a sulfonamido group or a cyano group, two or more ofR¹ to R⁶ may be bonded to each other to form a ring, when m is 2 orgreater, two of the groups R¹ to R⁶ may be bonded to each other, withthe proviso that the groups R¹ are not bonded to each other, n is anumber satisfying a valence of M, and X is a halogen atom, a hydrocarbongroup, an oxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residue, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural groups X may bethe same or different and may be bonded to each other to form a ring;and (B) at least one compound selected from the group consisting of:(B-1) an organometallic compound, (B-2) an organoaluminum oxy-compound,and (B-3) a compound which reacts with the transition metal compound(A″) to form an ion pair.
 18. The process of claim 17, wherein thetransition metal compound is represented by the following formula(III-a):

wherein M is a transition metal atom of Group 4 or Group 5 of theperiodic table, m is an integer of 1 to 3, R¹ to R⁵ may be the same ordifferent, and are each a hydrocarbon group, an alkoxy group or ahydrocarbon-substituted silyl group, R⁶ is a halogen atom, a hydrocarbongroup, a hydrocarbon-substituted silyl group, an alkoxy group, analkylthio group or a cyano group, two or more of R¹ to R⁶ may be bondedto each other to form a ring, when m is 2 or greater, two of the groupsR¹ to R⁶ may be bonded to each other, with the proviso that the groupsR¹ are not bonded to each other, n is a number satisfying a valence ofM, and X is a halogen atom, a hydrocarbon group, an oxygen-containinggroup, a sulfur-containing group, a nitrogen-containing group, ahalogen-containing group or a silicon-containing group, and when n is 2or greater, plural groups X may be the same or different and may bebonded to each other to form a ring.
 19. The process of claim 18,wherein m is
 2. 20. The process of claim 17, wherein the catalystfurther comprises a carrier (C).